AWT Fall Analyst 2021

the ANALYST The Voice of the Water Treatment Industry

Volume 28 Number 4

1300 Piccard Drive, Suite LL 14 • Rockville, MD 20850

Fall 2021

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling? Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

Volume 28 Number 4 Fall 2021

Can a New Type of Tagged Polymer Replace Inert Tracers and Provide Accurate Monitoring of Antiscalant and Dispersancy Treatments? How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process Published by

Cover A chemical feed process control system. Photo courtesy of Laith Charles, Watermark, LLC.

Fall 2021

Volume 28

Number 4

8 How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

Zahid Amjad, Ph.D., Walsh University

In this study, spontaneous precipitation technique was used to evaluate the influence of polymers with different architecture as calcium oxalate (CaOx) inhibitors. The polymers tested fall into three categories: 1. natural polymers, 2. carboxylate-modified biopolymers, and 3. synthetic polymers. Results reveal that polymer performance strongly depends on polymer dosage and architecture.

22 Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

Edward Beardwood, BC&T Inc.

This article will briefly discuss steam purity and steam generation system corrosion control. The overall emphasis will be on deposition control within steam generators and the application and expectations of the various types of internal chemical treatment programs that are available. Typically, as the operating pressures of the steam generators increase, the allowable impurity loadings decrease, requiring either improvements of feedwater and makeup water purity and/or increased blowdown rates to lower the carrying capacity of the steam generator.

34 Can a New Type of Tagged Polymer Replace Inert Tracers and Provide Accurate Monitoring of Antiscalant and Dispersancy Treatments?

Klin A. Rodrigues, Ph.D., and Jan Sanders, Nouryon Surface Chemistry

Inert tracers such as PTSA and fluorescein (typically used in boiler feedwater) are used by the AWT community to monitor the dosing of formulations into water treatment systems. While inert tracers can help water treaters to monitor how much formulation is being added and maintained in their systems, these tracers do not indicate how much polymer is being consumed. Different components in the formulation are depleted at different rates, and the use of an inert tracer does not provide an accurate picture of how much active polymer is available to provide scale control and dispersancy in the system.

4

Calendar of Events

5

President’s Message

6

Message From the President-Elect

52 Membership Benefits 54 Industry Notes 59 Amplify AWT 62 CWT Spotlight 63 Making a Splash 66 Tales From the Waterside 69 Life Beyond Water 73 T.U.T.O.R. 76 Business Notes 78 Advertising Index

46 How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process

Swati Sharma, Ph.D., Water Engineering Inc.

Sunflower oil refineries produce large quantities of fatty-acid-rich wastewater with a high concentration of organic pollutants. Sunflower oil wastewater is typically treated by dissolved air flotation (DAF) and chemical coagulation followed by anaerobic digestion. Over time, the efficiency of the DAF system is reduced due to a high influx of oily/fatty contents coming in at a large loading rate. As a result, the wastewater is either diverted from DAF to storage ponds or redirected to the anaerobic lagoons, thereby resulting in increased organic loads. Currently, electrochemical processes are being studied to find an alternative solution to these traditional treatment methods.

3 the ANALYST Volume 28 Number 4

1300 Piccard Drive, Suite LL 14 Rockville, MD 20850 (301) 740-1421 • (301) 990-9771 (fax) www.awt.org

2022 AWT Board of Directors President

Matt Jensen, CWT

Calendar of Events

Association Events 2022 Technical Training Seminars, West

Secretary

February 23–26, 2022 Hyatt Regency Lake Washington Seattle, Washington

Treasurer

2022 Technical Training Seminars, East

President-Elect

Stephen C. Hallier, CWT Noah Baskin

March 30–April 2, 2022 Cleveland Marriott Downtown at Key Tower Cleveland, Ohio

John D. Caloritis, CWT

Immediate Past President

Michael Bourgeois, CWT

Directors

Lee Browne Mark Coldren, CWT Kyle Rossi, CWT Fred Shurtz

2022 Business Owners Meeting

Ex-Officio Supplier Representative

September 20, 2022 Pan Pacific Vancouver Hotel Vancouver, Canada

Past Presidents

2022 Annual Convention & Exposition

Pam Simmons

Jack Altschuler John Baum, CWT R. Trace Blackmore, CWT, LEED AP Michael Bourgeois, CWT D.C. “Chuck” Brandvold, CWT Thomas Brandvold, CWT Brent W. Chettle, CWT Dennis Clayton Bernadette Combs, CWT, LEED AP Matt Copthorne, CWT James R. Datesh John E. Davies, CWT Jay Farmerie, CWT Gary Glenna Charles D. Hamrick Jr., CWT Joseph M. Hannigan Jr., CWT

Mark R. Juhl Brian Jutzi, CWT Bruce T. Ketrick Jr., CWT Bruce T. Ketrick Sr., CWT Ron Knestaut Robert D. Lee, CWT Mark T. Lewis, CWT Steven MacCarthy, CWT Anthony J. McNamara, CWT James Mulloy Alfred Nickels Scott W. Olson, CWT William E. Pearson II, CWT William C. Smith Marc Vermeulen, CWT David Wagenfuhr Casey Walton, B.Ch.E, CWT Larry A. Webb

Staff

Executive Director Heidi J. Zimmerman, CAE Deputy Executive Director Sara L. Wood, MBA, CAE Senior Member Services Manager Angela Pike Vice President, Meetings Grace L. Jan, CMP, CAE Meetings Planner Caroline Bentley Exhibits and Sponsorship Manager Brandon Lawrence Senior Director, Creative Services/Marketing Jennifer Olivares Marketing Coordinator Mary Claire Gordon Managing Editor Lynne Agoston Production Manager Maryia Alenchyk Director of Accounting Services Dawn Rosenfeld

The Analyst Staff

Publisher, Heidi J. Zimmerman, CAE Managing Editor, Lynne Agoston Production Manager, Maryia Alenchyk Technical Editor Michael Henley, mdhenleywater@gmail.com, (303) 745-3890 Advertising Sales Manager Carol Nettles, cnettles@awt.org

The Analyst is published quarterly as the official publication of the Association of Water Technologies. Copyright 2021 by the Association of Water Technologies. Materials may not be reproduced without written permission. Contents of the articles are the sole opinions of the author and do not necessarily express the policies and opinions of the publisher, editor or AWT. Authors are responsible for ensuring that the articles are properly released for classification and proprietary information. All advertising will be subject to publisher’s approval, and advertisers will agree to indemnify and relieve publisher of loss or claims resulting from advertising contents. Editorial material in the Analyst may be reproduced in whole or part with prior written permission. Request permission by writing to: Managing Editor, the Analyst, 1300 Piccard Drive, Suite LL 14, Rockville, MD 20850, USA. Annual subscription rate is $100 per year in the U.S. (4 issues). Please add $25 for Canada and Mexico. International subscriptions are $200 in U.S. funds.

September 21–24, 2022 Vancouver Convention Centre Vancouver, Canada

2023 Annual Convention & Exposition

October 4–7, 2023 Amway Grand Hotel and Grand Rapids Convention Center Grand Rapids, Michigan

Also, please note that the following AWT committees meet on a monthly basis. All times shown are Eastern Time. To become active in one of these committees, please contact us at (301) 740-1421. Second Tuesday of each month, 11:00 am – Legislative/Regulatory Committee
 Second Tuesday of each month, 2:30 pm – Convention Committee Second Wednesday of each month, 11:00 am – Business Resources Committee Second Friday of each month, 10:00 am – Special Projects Subcommittee
 Second Friday of each month, 11:00 am – Cooling Subcommittee
 Second Friday of each month, 2:00 pm – Pretreatment Subcommittee
 Third Monday of each month, 9:00 am – Certification Committee
 Third Monday of each month, 3:30 pm – Young Professionals Task Force Third Tuesday of each month, 3:00 pm – Education Committee
 Third Friday of each month, 9:00 am – Boiler Subcommittee
 Third Friday of each month, 10:00 am – Technical Committee Quarterly (call for meeting dates), 10:00 am – Wastewater Subcommittee

Other Industry Events

ASHRAE, AHR Expo, January 31–February 2, 2022, Las Vegas, Nevada BOMA, Winter Business Meeting, February 6–9, 2022, Washington, D.C. CTI, Annual Conference, February 6–10, 2022, Houston, Texas AMPP, Corrosion Risk Management Conference, March 6–10, 2022, San Antonio, Texas ACS, Spring National Meeting & Expo, March 20–27, 2022, San Diego, California WQA, Convention and Expo, April 6–8, 2022, Orlando, Florida AWWA, Annual Conference & Expo, June 12–15, 2022, San Antonio, Texas ASHRAE, Annual Conference, June 25–29, 2022, Toronto, Canada BOMA, International Conference and Expo, June 25–29, 2022, Nashville, Tennessee ASHE, Annual Convention & Expo., July 17–20, 2022, Boston, Massachusetts ACS, Fall National Meeting & Expo, August 21–25, 2022, Chicago, Illinois WEFTEC, Annual Exhibition and Conference, October 8–12, 2022, New Orleans, Louisiana IWC, Annual Conference, November 6–10, 2022, Orlando, Florida RETA, Annual Convention, November 7–10, 2022, Reno, Nevada

4 the ANALYST Volume 28 Number 4

President’s Message

By Matt Jensen, CWT

What a great meeting in Providence, Rhode Island! Thank you to everyone who attended. It was nice to see so many friends and visit with industry peers.

Supply Chain As I write this, the global supply chain continues to be in crisis. Raw materials are increasingly difficult to obtain, and the cost of shipping continues to increase. There is no easy answer to this complex set of problems, and it looks as if we will be living with this for some time to come. During these times, it has been more important than ever to stay connected to our AWT community. Some of the best resources I have found have been from my colleagues at AWT.

Amplify By now you have probably seen or heard about the Amplify AWT campaign, which is a discussion we encourage you to engage in over the coming months. This project came about when AWT began exploring options for addressing concerns facing the sustainability and health of the association. In short, current market forces, along with AWT’s structure, are inhibiting growth that would lead to long-term sustainability. A task force was established to evaluate potential changes we could make. The two current proposals are to change the cap on water treatment company members to 500 employees or fewer and to add an individual membership category. We need your input on these matters. If you have not participated in our town hall discussions, I encourage you to contact me at president@awt.org. Thank you for the opportunity to serve. I can be reached at president@awt.org.

Ask for Legiolert and deliver more accurate Legionella results The Legiolert® Test is a more accurate culture test for Legionella pneumophila Spread plate methods are notoriously inaccurate, with up to tenfold variability in results for the same sample.1 Multiple peer-reviewed studies have confirmed that the Legiolert Test provides more accurate and consistent results.2–5

See the difference the Legiolert Test can make at idexx.com/legiolertdifference. References

1. Lucas CE, Taylor TH Jr, Fields BS. Accuracy and precision of Legionella isolation by US laboratories in the ELITE program pilot study. Water Res. 2011;45(15):4428–4436. doi:10.1016/j.watres.2011.05.030 2. Petrisek R, Hall J. Evaluation of a most probable number method for the enumeration of Legionella pneumophila from North American potable and nonpotable water samples. J Water Health. 2018;16(1):25–33. doi:10.2166/wh.2017.118 3. Spies K, Pleischl S, Lange B, et al. Comparison of the Legiolert/Quanti-Tray MPN test for the enumeration of Legionella pneumophila from potable water samples with the German regulatory requirements methods ISO 11731-2 and ISO 11731. Int J Hyg Environ Health. 2018;221(7):1047–1053.doi:10.1016/j.ijheh.2018.07.006 4. Sartory DP, Spies K, Lange B, Schneider S, Langer B. Evaluation of a most probable number method for the enumeration of Legionella pneumophila from potable and related water samples. Lett Appl Microbiol. 2017;64(4):271–275. doi:10.1111/lam.12719 5. Barrette I. Comparison of Legiolert and a conventional culture method for detection of Legionella pneumophila from cooling towers in Québec. J AOAC Int. 2019;102(4):1235–1240. doi:10.5740/jaoacint.18-0245

© 2021 IDEXX Laboratories, Inc. All rights reserved. • 2485785-01 • All ®/TM marks are owned by IDEXX Laboratories, Inc. or its affiliates in the United States and/or other countries. The IDEXX Privacy Policy is available at idexx.com.

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5 the ANALYST Volume 28 Number 4

Message From the President-Elect

It was great to see so many of you in Providence, Rhode Island, for the 2021 Annual Convention & Exposition. By all accounts, the meeting was a big success. It was wonderful to see vendors, hear excellent papers, listen to informative Commercial Corner sessions, and network with colleagues. With that said, we are working hard to provide a truly amazing event next year for the 2022 AWT Annual Convention & Exposition, September 21–24, 2022, in Vancouver, Canada. Please join us!

Location If you haven’t been to Vancouver, you are in for a treat. Vibrant, pioneering, and surrounded by stunning natural backdrops, Vancouver is an unparalleled destination. Our hotels and the Vancouver Convention Center are located right downtown, making it a breeze to get to some of the city’s top attractions, many within walking distance. Whether you are interested in exploring Stanley Park or the city’s beaches, partaking in a spot of shopping or wandering a unique neighborhood, you can experience an authentic taste of Vancouver in a couple of hours or less. Vancouver showcases some of the world's most beautiful (and accessible) nature, offering year-round mountain, rainforest, and ocean excursions. This is a

By Steve Hallier, CWT

take-your-breath-away, choose-your-own-adventure kind of place. Plus, you'll find nonstop direct flights from hundreds of destinations, making it easy to get to. I’d encourage you to take extra time before or after the AWT Convention to explore all that the area has to offer.

Hotels The headquarters hotel is the Pan Pacific Vancouver Hotel. In addition, AWT has secured rooms at two other properties—the Marriott Vancouver Pinnacle Downtown and the Pinnacle Hotel Harborfront. All three hotels offer great amenities and a comfortable stay, right in downtown Vancouver and close to the Convention Center. Passport One final note about the 2022 Convention. Go ahead and pull your passport out now to check the expiration date. Your passport needs to be good through December 31, 2022, to gain entry for the Convention. And if you don’t have a passport, you’ll want to start that process now, as there are currently long wait times. As we continue to plan the 2022 Annual Convention, I welcome your feedback. I can be reached at steve@wetsolutionsinc.com. Thank you for the opportunity, and I look forward to serving you!

6 the ANALYST Volume 28 Number 4

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The Most Competitive Water Treatment Insurance Unfortunately, insurance costs for water treatment and chemical operations are increasing in 2021. The industry is a victim of the hardening insurance market. WaterColor has responded with new solutions to deliver to AWT members of all sizes, the lowest cost industryspecific coverages. WCM has underwriting authority and the access to multiple A-rated carriers to provide to you, in 50 states and Canada, the broadest policies at the lowest premiums. Our offerings include: • Commercial Auto & Hired & Non-Owned Auto • General, Products & Completed Operations, Errors & Omissions and Pollution Liability • No Contaminants Exclusions e.g. Legionella & other Pathogens, Mold, Corrosives, etc. • Pollution: On-site, Off-site & in Transit, up to $25m • Occurrence-based policies:- valid until the expiry of the statutes of limitations • Property, Inland Marine and Equipment Breakdown • Employee Fidelity, Cyber Extortion and Cyber Theft

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C

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling? Zahid Amjad, Ph.D., Walsh University

8 the ANALYST Volume 28 Number 4

Abstract

In this study, spontaneous precipitation technique was used to evaluate the influence of polymers with different architecture as calcium oxalate (CaOx) inhibitors. The polymers tested fall into three categories: 1. natural polymers (i.e., fulvic acid [FA], alginic acid [ALG], lignosulfonate [LS], green tea extract [GTE], starch [ST], and others); 2. carboxylate-modified biopolymers (i.e., carboxymethyl inulin with different degree of carboxylation [CMI]); and 3. synthetic polymers (i.e., homopolymers of acrylic acid, maleic acid and acrylic acid, maleic acid-based copolymers with different molecular weights [MW] and monomers with different functional groups). Results reveal that polymer performance strongly depends on polymer dosage and architecture. Based on the data obtained, the polymers may be ranked as follows: Natural polymers: FA > ALG, GTE, ST, LS Carboxylate-modified biopolymers: CMI-25 > CMI-20 > CMI-15 Synthetic polymers: homopolymers > co-, terpolymers In general, polymers containing carboxy (-COOH) group perform better than co- and terpolymers containing hydrophobic and bulky comonomers. Analysis of SEM and FT-IR data on the crystals grown in the absence of polymers reveal the formation of COM (calcium oxalate monohydrate) as the predominant phase. Results also indicate that the presence of polymers in CaOx supersaturated solution favor the formation of calcium oxalate dihydrate (COD).

Introduction

In industrial water systems, scaling may be defined as a solid layer deposition on equipment surfaces. Scale is formed when hard water is heated or cooled in heat transfer equipment such as heat exchangers, condensers, evaporators, cooling towers, boilers, pipes and pumps. The type of scale differs, depending on the mineral content of the available water. Many feed waters contain alkaline earth metal cations (i.e., calcium, magnesium, barium, and strontium, among others) and anions (i.e., carbonate, bicarbonate, phosphate, and others).

When combinations of these cations and anions exceed their solubility product of the various species, precipitate (or scale) forms until the respective solubility products are no longer exceeded. Types of mineral salt (scale) typically encountered in industrial systems include calcium carbonate, calcium phosphate, calcium sulfate, calcium fluoride, silica, metal silicates, calcium oxalate, and others. Scaling continues to present serious operational challenges in all chemical industries, such as sugar processing, semiconductor manufacturing, pulp and paper mills, food processing, oil and gas production, power generation, and geothermal energy plants. Scale interferes with heat transfer by forming an insulating layer on heat exchange surfaces. Scale also interferes with water flow and promotes localized corrosion. As a result, scale formation may result in huge economic loss due to unscheduled shutdowns, premature equipment replacement, and reduced heat transfer (1). In desalination of brackish/seawaters by the reverse osmosis (RO) membrane-based process, the scaling of RO membrane surfaces is very common. In some industries, the periodic cleaning of membranes is routinely practiced, leading to high operational costs. Periodic cleaning has an adverse impact on the process economics and equipment involved. Tens and millions of dollars are spent every year to prevent and/or clean RO membranes in the water purification plants. Therefore, prevention of scale in an RO system is of paramount importance in the efficient operation of the system (2). Calcium oxalate (CaC2O4, CaOx) is a naturally occurring mineral found in plants and fossils. Plants commonly produce oxalic acid and calcium oxalate precipitates that are believed to regulate bulk-free calcium within the plants (3). The mineralization of CaOx has posed a significant problem to both biological and industrial systems. In the mammalian urinary tract, supersaturation of oxalate ions can cause the crystallization and aggregation of calcium oxalate salt, creating urinary stones. Three types of hydrated calcium oxalates—the monohydrate (CaC2O4.2H 2O, COM), the dihydrate (CaC2O4.2H 2O, COD), and the calcium oxalate trihydrate (CaC2O4.3H 2O, COT)—are found in urinary stones. COD and COT are thermodynamically unstable relative to COM under renal conditions, and it is the main constituent of kidney, gall, and bladder stones (4).

9 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

In addition to biological frequencies, CaOx is encountered as deposits on equipment surfaces, such as in paper making, sugar processing, brewing, and water operations. In Australian sugar mills, the most important intractable scales forming in the late stages of the evaporation process are COM and COD and silica (5). COM and COD together make up about 50 weight percentage (wt %), and silica accounts for about 30 wt % of all scale formed in the fourth and fifth effects. COM, having high heat capacity (153 joules per kelvin [J/K]) makes an effective insulator between the heat transfer surfaces and the sugar juice inside the tubes. The sources of COM and COD in sugar milling are primarily calcium hydroxide (added to the juice in the clarification stage), and oxalic acid, which is both present originally in the sugar cane and formed in situ by oxidation of sucrose (5). In the beet sugar industry, CaOx deposition in evaporators is a persistent problem. Factors contributing to CaOx scale formation at beet sugar plants include increased sugar contents, higher oxalic acid concentration, and lower temperature (6). In water-related industries, CaOx forms scale deposits on heat exchangers and RO membrane surfaces. The deposition of scales on heat exchanger and membrane surfaces is a serious problem, often impairing significantly on the overall process and in all cases increasing the cost of production due to the concomitant maintenance costs. The effect of pyrophosphate and phosphonate anions on the spontaneous formation of COM, COD, and COT has been investigated in supersaturated solutions of lowand high-ionic strength in solutions simulating physiological urine conditions. The rate of crystal growth in the presence of these additives was found to be dependent on the square of solution supersaturation. Results suggested that calculated rate constants for COT were independent of additive concentration of both the pyrophosphate and phosphonate cases. Additionally, pyrophosphate decreases the nucleation kinetics of COM (7). The influence of additives as CaOx inhibitors has been the subject of numerous investigations by academic researchers and industrial technologists. Campbell et al. (8) investigated the influence of polyelectrolytes and proteins as CaOx inhibitors under supersaturation

continued

“In the beet sugar industry, CaOx deposition in evaporators is a persistent problem.” conditions. Results indicated that polyelectrolytes and proteins may behave differently when free in solution or when immobilized on a surface. Akyol and co-workers (9) investigated the effects of polyelectrolytes on the inhibition and aggregation of CaOx crystallization. Results revealed that the acidic acrylate block copolymers inhibited crystal growth through the adsorption onto active growth sites. In other work, Bouropoulos et al. (10) studied the effect of maleic acid copolymers on the seeded growth COM. Results of this investigation showed that reduction in COM crystal growth strongly depends on the nature of comonomer polymerized with maleic acid. In addition, it was also observed that the morphology of COM was unaffected, yet the crystals growing at lower rates in the presence of copolymers were larger and their size more uniform. Wallace and co-workers who investigated the impact of end-group functionality and molecular weight (MW) reported that the extent of CaOx inhibition was in general dependent on the hydrophobicity and the MW of the end group (11). In another study by Kweik and Amjad, it was shown that the type of monomer plays an important role on the inhibitory activity of the polymer (12). The present work reported in this article is a quantitative investigation of the effects of polymers with different molecular architecture on the inhibition of CaOx in aqueous solution. The polymers tested fall into three categories: 1. natural (e.g., lignosulfonate, green tea extract, fulvic acid, alginic acid, starch); 2. carboxylate-modified biopolymers (e.g., inulin with different degrees of carboxylation); and 3. synthetic (e.g., homo-, co-, and terpolymers). It is hoped that the performance data presented herein will help water technologists in developing new treatment formulations for systems where CaOx scale presents serious operational challenges.

10 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

Experimental Materials Stock solutions of sodium oxalate (Na 2C2O4) and calcium chloride (CaCl 2.2H 2O) were prepared from respective crystalline solids using distilled water, filtered through 0.22-micron (µm) filter paper, and analyzed by ion chromatography and atomic absorption spectrometry, respectively. The polymers tested were commercial and experimental materials, and stock solutions of these polymers were prepared on dry weight basis. The required concentration was achieved by dilution. Calcium Oxalate Precipitation Protocol Supersaturated solutions of calcium oxalate for precipitation experiments were prepared by adding a known volume of stock solutions of sodium oxalate and inhibitor solutions to glass bottles containing known volume of distilled water maintained at 25 ºC. Following temperature equilibration, a known volume of calcium chloride stock solution was added in such amount to achieve required supersaturation. The progress of CaOx precipitation in the absence and presence of inhibitor was followed by measuring the conductivity (Orion Star A212 conductivity meter) as a function of inhibitor concentration and time. The inhibitor performance was calculated using Equation 1. Percent Inhibition (%I) = [(C)c – (C)b] / [(C)a – (C)b] x 100 Eq. 1 Where: (C)a = conductivity in the presence of inhibitor at known time (C)b = conductivity at the beginning of experiment [(C)c = conductivity in the absence of inhibitor at 20 hours (hr) At the end of the experiments, solid samples of precipitates were collected for characterization by scanning electron microscopy (SEM, JEOL, JSM 5200). In all experiments, calculations for driving force were done by considering all appropriate equilibria between calcium, oxalate, and the inhibitor species in solutions using the computational software as reportedly previously (10, 12).

continued

The driving force for calcium oxalate precipitation in aqueous supersaturated solutions is defined as the change in Gibbs free energy going from the supersaturated solution to the equilibrium (10). This is illustrated in Equation 2.

Eq. 2

In Equation 2, R is a gas constant, T the absolute temperature, K 0sCOM the thermodynamic solubility of COM, and the ( ) denote the activities of the corresponding ions. The ratio in the logarithmic term is the supersaturation ratio. As may be seen in Equation 2, the supersaturation ratio included in the logarithmic term determines the deviation of the system—in our case, the supersaturated solution—from equilibrium, which is determined by the activity product of the salt that precipitates. For positive deviation from equilibrium (activity product of the salt ions larger than the corresponding at equilibrium), ∆G < 0, and the formation of the respective solid may take place spontaneously. Results of duplicate or triplicate experiments showed good reproducibility (± 7%). The scaling index (SI) as calculated using the formula Log (IP/Ksp) for Ca = Ox = 0.45 millimolar (mM) is 1.52, 1.17, and 1.00 for COM, COD, and COT, respectively, indicating that calcium oxalate solution is supersaturated with respect to all CaOx phases.

Results and Discussion

Water available for domestic (e.g., laundry, dishwashing, cleaners) and industrial (e.g., cooling, boiler, desalination, geothermal, oil and gas production) applications is not pure but contains a variety of soluble and insoluble impurities. To overcome challenges caused by these impurities, additives (i.e., polyphosphates, phosphonates, and polymers containing various functional groups, among others) are used in the formulations for a variety of reasons, but most importantly, they are used as scale inhibitors, dispersants, cleaners, metal ions stabilizers, anti-spotting agents, and anti-deposition agents.

11 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

Additives prevent scale formation either by adsorbing onto crystal growth sites of micro-crystallites, thereby interfering with crystal growth, or by retarding or completely suppressing the formation of critical nuclei in the supersaturated fluid. Adsorption at specific sites of the growing crystals may result in changes in crystal morphology on the slower growing crystals.

Polymers Performance as CaOx Inhibitors Using the experimental protocol described previously, a series of experiments was carried under standard test conditions in the presence of various polymers. The polymers tested include: Natural materials such as lignosulfonate green tea extract, fulvic acid, alginic acid, starch, and others. Carboxylate-modified inulin with different degrees of carboxylation. Synthetic polymers such as homopolymers of acrylic acid, maleic acid, itaconic acid, methacrylic acid, and copolymers containing monomers with different functional groups and MW.

Natural Polymers Natural polymers (i.e., starches, lignosulfonates, aliginates, and natural organic polyelectrolytes, including humic, fulvic, and tannic acids) were evaluated for their efficacy as CaOx inhibitors. Natural organic polyelectrolytes such as tannic substances are commonly encountered in surface and groundwater water supplies. Humic substances are generally considered to be composed of operationally three distinct fractions: 1. fulvic acid (FA), which is soluble in both acidic and basic solutions; 2. humic acid, which is soluble in basic solutions, but insoluble in acidic solutions; 3. humin, which is insoluble in both acidic and basic solution.

continued

The bulk of humic substances in river water generally resembles more readily solubilized FA, with relatively less soluble humic acid, and these substances are likely dependent on the pH of the natural water. Natural polymers such as starches, alginates, and lignosulfonates have been used for years to disperse particulate matter in industrial water systems. These polymers function as dispersants, but their performance is very sensitive to the high temperature normally encountered in treating boiler water. Lignosulfonates (LSs) are chemically modified biopolymers that are produced during the production of cellulose with the use of sulfites. The biopolymer basis of LS is lignin, found in wood and other plants. The structure of LS contains two functional groups (phenolic [-OH] and sulfonic acid [-SO3H]) responsible for surface-active properties. Figure 1 lists the structures and functional groups of natural polymers tested. To evaluate the performance of natural polymers containing different functional groups (e.g., -OH, -SO3H, carboxy group [-COOH]), a series of precipitation experiments was carried under similar experimental conditions (Ca = Ox = 0.45 mM) and in the presence of 2.5 and 10 milligram per liter [mg/L] inhibitor. Results calculated according to Equation 1 are presented in Figure 1: List of natural polymers tested.

12 the ANALYST Volume 28 Number 4

­

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

Figure 2. Data show that all polymers tested at low concentrations (i.e., 2.5 mg/L) exhibit poor performance (<10% I). It can be seen that whereas increasing the polymer concentration by four-fold (i.e., 2.5 to 10 mg/L) does not exhibit any performance improvement for AL, ST, GTE, and LS (<10% I), FA, on the other hand shows significant improvement in polymer performance (8% to 28%). The increased FA performance compared to AL, ST, GTE, and LS may be attributed to the presence of -COOH and low MW. It is worth noting that whereas LS shows poor performance as CaOx inhibitor, LS has been shown to exhibit better performance as iron oxide dispersants compared to AG, ST, FA, and GTE (13). Additionally, in another study on calcium carbonate (CaCO3) inhibition, it has been observed that whereas FA and GTE show poor performance as CaCO3 inhibitors, these polymers exhibit strong influence on CaCO3 crystal morphology (14). Figure 2: Calcium oxalate inhibition in the presence of varying dosages of natural polymers.

Figure 3: Structure of carboxylate-modified biopolymer, CMI.

Functional Groups

continued

Figure 4: Calcium oxalate inhibition in the presence of varying dosages of carboxylate-modified biopolymers.

Carboxylate-Modified Biopolymers The effect of a biodegradable, environmentally friendly polysaccharide-based polycarboxylate, carboxymethyl inulin (CMI), was investigated as a function of dosage under similar CaOx supersaturation. Figure 3 shows the chemical structure of CMI. Figure 4 presents performance data for CMI-15, -20, and -25 (where -15, -20, and -25 mean different degree of carboxylation). The MW of CMI-15, CMI-20, and CMI-25 are 3,500, 4,000, and 4,500, respectively. As illustrated, CMI performance as CaOx inhibitor depends on polymer concentration, degree of carboxylation, and MW. Data presented in Figure 4 clearly show that CMI performance increases with increasing CMI concentration, degree of carboxylation, and MW. Based on the data shown in Figure 4, CMI performance can be ranked as follows: CMI-25 > CMI-20 > CMI-15. It should be noted that a similar performance trend as observed in the present study has been reported for calcium carbonate, calcium sulfate, and strontium sulfate scales (15–17). Synthetic Polymers Over the last few decades, a variety of acrylic acid, maleic acid, aspartic acid, and itaconic acid-based homo- and copolymers have been developed to treat various scaling and deposit problems in industrial water installations, including boiler, cooling, desalination, geothermal, and oil and gas production. These polymers serve three objectives: 1. to inhibit precipitation of scaleforming salts; 2. to complex metal ions and/or stabilize/ disperse metal hydroxides (e.g., copper [Cu], manganese [Mn], zinc [Zn], iron [Fe], aluminum [Al]); and 3. to disperse suspended matter (i.e., corrosion products such as clay, silt, precipitated salts, and others). In the case of supersaturated solutions of sparingly soluble salts,

14 the ANALYST Volume 28 Number 4

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How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

continued

polymer interferes with the nucleation and crystal growth processes via the interactions of metal ions (e.g., Ca, Mg, Ba, Sr) with the functional groups (e.g., -COOH, -SO3H, - CON [R1, R2], -COOR) present in the polymer. The metal ion-polymer interactions not only delay the precipitation of scale-forming salts, but in some cases, polymer also influences the crystal morphology of the scale crystals. Figure 5 presents the structure, monomer functional group, and MW of homopolymers of acrylic acid, methacrylic acid, maleic acid, itaconic acid, epoxysuccinic acid, and 2-methyloxazoline. It can be seen that polymers vary significantly in terms of architecture, monomer type, monomer functional group, and MW. Figure 5: Analytical characteristics of homopolymers tested.

Figure 6 presents performance data on PAA and PMAA as a function of dosage. There are two points worth noting: 1. %I value increases with increasing polymer concentration, and 2. substituting -H in PAA with methyl (-CH3) group (e.g., PMAA) decreases polymer performance. The decreased performance shown by PMAA compared to PAA may be attributed to interference by the -CH3 group present in the adsorption of PMAA of CaOx crystallites. Figure 6 also presents data on poly(2-ethyloxazoline), PEOX. It is interesting to note that whereas PEOX is an ineffective inhibitor for CaOx, this polymer has been shown to be an excellent inhibitor for silica scale (18). Performance data on all homopolymers tested is presented in Figure 7. Based on the data, polymers can be ranked as follows: PIA > PESA ≈ PAA ≈ PMA > PMAA >> PEOX. The influence of ionic charge of the functional group (i.e., acidic, -SO3H; neutral, - N-C=O) present in copolymers of maleic acid as a function of polymer dosage is illustrated in Figure 7. It can be seen that polymer performance improves with increasing polymer concentration. Additionally, partially replacing a maleic acid monomer with a -SO3H group containing a monomer (i.e., sulfonated styrene) and neutral group containing a monomer (i.e., pyrollidone) reduces the copolymer performance to a varying degree. For example, %I value obtained in the presence of 5 mg/L PMA is 65% compared to 45 and 25% obtained for PMVP and PMSS, respectively. The poor performance shown by PMSS compared to PMVP may be attributed to MW and monomer ratios.

16 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

Figure 6: CaOx inhibition by homopolymers as a function of dosage.

continued

Figure 7: CaOx inhibition by homopolymers with different functional groups at 5 mg/L polymer dosage.

The composition of various copolymers containing different functional groups tested are shown in Figure 8. Figure 8: Analytical characteristics of copolymers evaluated.

Figure 9 shows the comparative performance data collected in the presence of 5 mg/L of a variety of copolymers containing different functional groups. Data clearly show that partially replacing acrylic acid or maleic acid with a second monomer containing different functional groups (i.e., -SO3H, -COOR) significantly reduces the performance of co- and terpolymers. It is worth noting that whereas AA- and MA-based copolymers show poor performance for CaOx, these polymers have been reported to exhibit good to excellent performance as calcium phosphate and calcium phosphonate inhibitors and also as iron oxide dispersants. Thus, it is clear that polymer performance as a scale inhibitor and/or a dispersant strongly depends on the polymer architecture and industrial system being treated. The effect of MW on polymer performance is presented in Figure 9 for two copolymers (PMVP1, MW 15,000; PMVP2, MW 60,000).

17 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

continued

Figure 9: CaOx inhibition by copolymers at 5 mg/L dosage.

Calcium Oxalate Crystal Morphology Characterization The results discussed above show that low concentrations of certain polymers markedly reduce the precipitation of calcium oxalate from aqueous solutions. The impact of these polymers on the precipitation process may be explained in terms of three effects: 1. polymers may change the ionic strength of calcium oxalate solution and hence the effective solubility of calcium oxalate; 2. direct complexation of polymer with calcium ions in solution; and 3. adsorption of polymer on calcium oxalate crystallites.

Hahn and Robertson (19) and Amjad (20) have described the importance of polymer architecture to polymer effectiveness of dispersion of particulate matter and calcium phosphate inhibition. For a polymer to effectively disperse particulates and inhibit/ disperse calcium phosphate, the polymer adsorbs on the particle surface and provides steric or electrostatic particle-particle interaction so that agglomeration does not occur. The authors suggested that co- and terpolymers containing acidic and/or non-ionic groups as being ideally suited for dispersion of iron oxide and calcium phosphate. The weakly acidic acrylic acid units adsorb onto particulates, while the strongly acidic and ionized sulfonic acid groups provide chain extension into bulk water and enhance electrostatic repulsion. It is interesting to note that the reverse is true for crystalline sparingly soluble salts such as CaF 2 (21), SrSO4 (16), where homopolymers exhibit better performance compared to co- and terpolymers.

Under the experimental conditions employed in the present investigation, the marked reduction in calcium oxalate precipitation may be attributed to surface adsorption factor rather than calcium-polymer complex formation (the amount of calcium complex, even at highest concentration, accounts for less than 5% of total calcium), or the concomitant increase in ionic strength of the supersaturated solution in the presence of polymers. In this work, SEM was used to characterize the morphology of the CaOx crystals formed in the absence and presence of polymers. Figure 10A presents a micrograph of CaOx crystals formed in the absence of polymer. In all control experiments, COM was the predominant phase formed in CaOx supersaturated solution. However, as shown in Figure 10B, in the presence of 2.5 mg/L PESA, bipyramidal COD crystals were formed. It should be noted that COD crystals have been reported for CaOx crystals grown in the presence of additives (9).

Figure 10: Scanning electron micrographs of calcium oxalate grown in the absence (left) and in the presence (right) of 2.5 mg/L of PESA.

A

18 the ANALYST Volume 28 Number 4

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How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

continued

8. Campbell, A.A.; Ebrahimpour, A.; Perez, L.; Smesko, S.A.; Nancollas, G.H. (1989). “The Dual Role of Polyelectrolytes and Proteins as Mineralization Promoters and Inhibitors of Calcium Oxalate Monohydrate,” Calcified Tissue International, 45, pp. 122-128.

“The results discussed show that low concentrations of certain polymers markedly reduce the precipitation of calcium oxalate from aqueous solutions.”

9. Akyol, E.; Bozkurt, A.; Oner, M. (2006). “The Effects of Polyelectrolytes on the Inhibition and Aggregation of Calcium Oxalate Crystallization,” Polymers for Advanced Technologies. 17, pp. 58-65. 10. Bouropoulos, K.; Bouropoulos, N.; Melekos, M.; Koutsoukos, P.G.; Chitanu, G.C.; Anghelescu-Dogaru, A.G.; Carpov, A.A. (1998). “The Inhibition of Calcium Oxalate Monohydrate Crystal Growth by Maleic Acid Copolymers,” Journal of Urology, 159, pp. 1755-1761.

Summary

Successful water treatment programs incorporate effective scale inhibitors that are typically synthetic polymers. Although natural and biopolymers evaluated in the present study do show poor-to-mediocre activity, these polymers are not commonly used due to potential degradation under harsh system operating conditions. The results presented in this study show the following order of polymer effectiveness as calcium oxalate inhibitor: Homopolymers (containing -COOH) > copolymers > biopolymer > natural polymer. Additionally, it has been observed that the presence of synthetic polymer in calcium oxalate supersaturated solution favors the formation of calcium oxalate dihydrate compared to calcium oxalate monohydrate formed in the absence of polymer.

11. Wallace, A.D.; Al-Hamzah, A.; East, C.P.; Doherty, W.O.S.; Fellows, C.M. (2010). “Effect of Poly(acrylic acid) End-Group Functionality on Inhibition of Calcium Oxalate Crystal Growth,” The Journal of Applied Polymer Science, 116, pp. 1165-1171.

12. Kweik, A.; Amjad, Z. (2019). “Study on the Effect of Polymer Architecture in Inhibiting Calcium Oxalate Precipitation,” Paper No. 13014, CORROSION 2019, Houston, Texas (2019).

13. Amjad, Z. (2017). “Iron Oxide Dispersants for Industrial Water Systems: Types, Performance, and Selection Criteria,” International Journal of Corrosion and Scale Inhibition 6(2), pp. 162-179. 14. Amjad, Z. (2006).“Influence of Natural and Synthetic Additives on Calcium Carbonate Precipitation and Crystal Morphology,” Tenside Surfactants Detergents 43(4), pp. 184-190.

15. Verraest, G.I.; Peters, J.A.; van Bekkum, H.; Rosmalen, G.M. (1996). “Carboxymethyl Inulin: A New Calcium Carbonate Inhibitor,” Journal of the American Oil Chemists' Society 73(1), pp. 55-62. 16. Amjad, Z. (2012). “Gypsum Scale Inhibition Using Biopolymers and Synthetic Polymers,” Materials Performance 51(10), pp. 48-52.

17. Amjad, Z.; Kweik, A. (2019). “Comparative Performance of Natural, Hybrid, and Synthetic Polymers Containing Different Functional Groups as Strontium Sulfate Scale Inhibitors,” Paper No. 12880, CORROSION 2019, Houston, Texas. 18. Neofotistou, E.; Demadis, K. (2004).“Use of Antiscalants for Mitigation of Silica (SiO2) Fouling and Deposition: Fundamentals and Applications in Desalination Plants,” Desalination 167, pp. 257-272. 19. Hahn, W.M.; Robertson, S.T. (1990). “Control of Iron and Silica with Polymeric Dispersants,” Paper No. IWC 90-29, International Water Conference, Pittsburgh, Pennsylvania.

Acknowledgements

The author thanks Walsh University for its support in carrying out this study and Professor Peter G. Koutsoukos, University of Patras, Patras, Greece, for help in characterizing calcium oxalate crystals.

20. Amjad, Z. (1998). “Development of Calcium Phosphate Inhibiting Polymers for Cooling Water Applications,” Chapter 16 in Calcium Phosphates in Biological and Industrial Systems,” Z. Amjad, ed., Kluwer Academic Publishers, Boston, Massachusetts.

21. Amjad, Z. (2014). “Biopolymers as Calcium Fluoride Precipitation Inhibitors for Aqueous Systems, Chapter 6 in Mineral Scales in Biological and Industrial System, CRC Press, Boca Raton, Florida (2014).

References

1. Amjad, Z.; Demadis, K. (eds.) (2015). Mineral Scales and Deposits: Scientific and Technological Approaches, Elsevier Publisher, Amsterdam, Netherlands. 2. Amjad, Z.; Workman, K.; Castete, D. (1993). “Considerations in Membrane Cleanings,” Chapter 7 in Reverse Osmosis: Membrane Technology, Water Chemistry, and Industrial Applications,” Van Nostrand Reinhold, New York, NY. 3. Franceschi, V.R.; Horner, H.T. (1980). “Calcium Oxalates in Plants,” Botanical Review, 46, pp. 361-427.

4. Khan, S.R. (1996). “Association Between Calcium Phosphate and Calcium Oxalate Crystals in the Development of Urinary Stone,” Chapter 21 in Mineral Scale Formation and Inhibition, Z. Amjad, ed., Plenum Press, New York, NY. 5. Doherty, W.O.S. (2006). “Effect of Calcium and Magnesium Ions on Calcium Oxalate Formation in Sugar Solution,” Industrial & Engineering Chemistry Research 45(2), pp. 642-647. 6. Gill, J.S. (1999). “The Influence of Scale Inhibitors on Calcium Oxalate Precipitation,” Paper No. 109 CORROSION 1999, Houston, Texas. 7. Gardner, G.L. (1978). “Effect of Pyrophosphate Anions on the Crystal Growth Kinetics of Calcium Oxalate Monohydrate,” Journal of Physical Chemistry 82(8), pp. 864-869.

Glossary of Abbreviations

Al: aluminum ALG: alginic acid CaCl 2.2H 2O: calcium chloride dihydrate CaCO3: calcium carbonate CaOx (also CaC2O4): calcium oxalate CMI: carboxymethyl inulin COD: calcium oxalate dihydrate (CaC2O4.2H 2O) COM: calcium oxalate monohydrate (CaC2O4.2H 2O) -COOH: carboxy COT: calcium oxalate trihydrate (CaC2O4.3H 2O) Cu: copper FA: fulvic acid Fe: iron

20 the ANALYST Volume 28 Number 4

How Do Different Polymers Compare in Inhibiting Calcium Oxalate Scaling?

J/K: joules per kelvin LS: lignosulfonate mg/L: milligram per liter mM: millimolar Mn: manganese MW: molecular weight Na 2C2O4: sodium oxalate -OH: phenolic RO: reverse osmosis SEM: scanning electron microscopy -SO3H: sulfonic acid ST: starch wt %: weight percent Zn: zinc µm: micron

continued

Zahid Amjad, Ph.D., is a visiting professor in chemistry at Walsh University, N. Canton, Ohio. He has more than 40 years of experience in water-soluble polymer research. Dr. Amjad has an M.Sc. degree from Punjab University and a doctorate from Glasgow University and was a post-doctoral fellow at the State University of New York at Buffalo. He has been a NACE member for more than 40 years. Dr. Amjad is a NACE Fellow and received a NACE 2016 Technical Achievement Award and NACE’s 2021 Distinguished Service Award. In 2002, he received the Association of Water Technologies’ 2002 Ray Baum Memorial Water Technologist of the Year Award. He holds 30 U.S. patents, has published more than 150 papers and articles, and has edited nine books. Dr. Amjad may be contacted at zamjad@walsh.edu.

21 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators? Edward Beardwood, BC&T Inc.

22 the ANALYST Volume 28 Number 4

Introduction

The management and control of boiler feedwaters and boiler waters are dependent on the control of steam purity, corrosion, and deposition within the steam-generating system. Practices or guidelines (1–8) have been developed to minimize the penalties of severe corrosion (or deposition), frequent cleaning requirements, or unscheduled outages in steam-generating systems and their auxiliary steam users. Other guidelines are available for pure utility-based steam-generation systems operating above 1,000 pounds per square inch gauge (psig) to super critical pressures (i.e., >3,200 psig) (9–11). While some manufacturers of waste heat and specialty boilers have their own guidelines, they typically are hybrids of those already available. These are not part of the scope of this article and will not be discussed. This article will briefly discuss steam purity and steam generation system corrosion control. The overall emphasis will be on deposition control within steam generators and the application and expectations of the various types of internal chemical treatment programs that are available. Typically, as the operating pressures of the steam generators increase, the allowable impurity loadings decrease, requiring either improvements of feedwater and makeup water purity and/or increased blowdown rates to lower the carrying capacity of the steam generator. External pretreatment and contaminant removal is always more reliable and usually more economical than higher levels of internal treatment chemicals and higher blowdown rates. That is, internal chemical treatments are used as polishing agents to minimize corrosion and deposition within the steam-generating system. Table A provides a general illustration of operating pressure and the potential for internal boiler corrosion or deposition to occur. The corresponding hydroxide alkalinities and pH for these corrosion and deposition categories can

“Steam purity is based on the number of contaminants present in the steam, and steam quality is based on the amount of moisture or water in the steam.”

be found in Table B. Equivalents per million of OH (hydroxide) alkalinity are denoted by EPMOH and can be used to determine vaporous carryover of silica (12). Table A: Deposition and Corrosion Operating Concerns Pressure Category

Operating Pressure Range (psig)

Internal Boiler Issue

Low

5–300

Deposition

Low

301–600

Deposition

Medium

601–750

Deposition & corrosion

Medium

751–900

Corrosion & deposition

High

>901

Corrosion

Table B: Corresponding pH and Alkalinities Associated With Corrosion and Deposition Avoidance Equivalents per Million Hydroxide Alkalinity, mg/L as OH

Aids in Avoiding

pH

OH Alkalinity, mg/L as CaCO3

Corrosion

9.0

0.5

0.010

Corrosion

9.5

1.6

0.032

Corrosion

10.0

5.0

0.100

Corrosion

10.3

10.0

0.200

Corrosion & scale

10.5

15.0

0.320

Scale deposits

11.0

50.0

1.0

Scale deposits

11.5

168

3.36

Scale deposits

12.0

500

10.0

Scale deposits

12.2

800

16

Notes: EPMOH = 1,000 X 10^ (pH–14); EPMOH = Hydroxide alkalinity mg/L as CaCO3 X 0.02

Steam Purity

Steam purity is based on the number of contaminants present in the steam, and steam quality is based on the amount of moisture or water in the steam. Restrictions due to direct steam contact with the process, be it a catalyst, reactor heating, steam reforming (hydrogen production), air humidification, food production of food packaging products, and others, are typically site specific and set by the producer. Other steam purity requirements are those put in place to protect boiler superheaters, steam-driven process equipment (i.e., blowers and fans operated by steam), and/or steam turbine drives, whether it is a condensing or back-pressure operation. These later restrictions have been set by

23 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

continued

original equipment manufacturers (OEM) consensus, and the total dissolved solids (TDS) in the saturated steam are typically as follows: Steam generators with no superheaters; TDS ≤ 1.0 milligrams per liter (mg/L). Steam generators with superheaters and operating less than 751 psig; TDS ≤ 0.3 mg/L. Steam generators with superheaters and operating greater than 751 psig; TDS ≤ 0.1 mg/L. Figure 1: Drawing of a boilers steam drum internals.

Figure 1 shows a schematic of a boiler’s steam drum internals and the features that help to improve the steam purity. While the steam purity for various turbine duties varies, the OEM can set their acceptable operating steam purity limits. Additional information regarding industrial turbines without reheat can be found in IWC Paper-14-28 (13). Monitoring steam purity (ASTM D–1066 and ASME PTC 19.11) (14, 15) is done with continuous analyzers for sodium (ASTM D - 2791) (16) and silica (ASTM D 859) (17) with the option to also analyze for degassed cation conductivity (ASTM D–4519) (18). The latter affords deeper troubleshooting capabilities. The generally acceptable steam contamination limits for industrial turbines are as follows:

24 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

TDS ≤ 60 micrograms per liter (µg/L) (i.e., 0.06 mg/L). Sodium + Potassium ≤ 20 µg/L (i.e., 0.02 mg/L) as Na + K. Silica ≤ 20 µg/L (i.e., 0.02 mg/L) as SiO2. Degassed Cation Conductivity ≤ 1.0 µS/cm. These limitations are to prevent corrosion (stress corrosion cracking [SCC]) and fouling (deposition) of superheaters and turbines leading to overheating and rotational inefficiency, respectively.

External Pretreatment

Physical and chemical external treatment of raw waters prior to use within the steam-generation system is always practiced. If the water supply is not from a municipal source, then clarification, filtration, and oxidation must be performed first. The type of secondary pretreatment will depend on the steam purity restrictions present at the site and the operating pressure of the steam generators. These pretreatments may be as follows: Organics and suspended solids removal via ultrafiltration. Noncondensable gases (i.e., oxygen, carbon dioxide, sulfur dioxide, hydrogen sulfide, nitrogen, and ammonia) and volatile organic carbons (VOC) via degasification. The pH may be adjusted to maximize the amount of the impurity to remain in a nonionizable state for stripping.

continued

“Physical and chemical external treatment of raw waters prior to the use within the steamgeneration system is always practiced.” In some cases, the boiler water alkalinity may be the limiting factor. To avoid excessive blowdown, dealkalizing can be performed. The dealkalizing step will remove the free carbon dioxide and the carbonate and bicarbonate alkalinity. This, in turn, will allow for higher feedwater cycles and less condensate return line corrosion inhibitor treatments as well as a reduction in blowdown flow. The hydroxide (OH) alkalinity and carbon dioxide produced from boiling softened water can be estimated by following the calculations provided in Table D. Assume the OH alkalinity is 80% of the “P” alkalinity tested. As the purity of the makeup water increases, the buffering capacity decreases. High-purity water will respond to anions by lowering the pH (i.e., acidizing anions) and cations by raising the pH (i.e., alkalizing cations). Either case can lead to internal boiler corrosion. Figure 2: An ion exchange treatment system.

Inorganic ionic impurities via reverse osmosis and/or ion exchange. Figure 2 shows an example of an ion exchange system, while Figure 3 shows a reverse osmosis system in a power plant application. If the pretreatment does not provide enough impurity reduction to operate within the steam purity limits, then either increased blowdown of the boiler water will be required or an upgrade in the pretreatment process will be needed. Table C can be used to provide guidance for such upgrades.

25 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

continued

Figure 3: An RO system such as might be found in a power plant.

Table C: Pretreatment Configurations and Estimated Effluent Conductance Purity

Key

Estimated Specific Conductivity, µS/cm

Treatment Process

Low purity

A

Raw Water Conductivity

Sodium form cation exchange softening (a).

B

Raw Water Conductivity + (0.53 µS/cm/mg/L) X (mg/L HCO3 Removed) (b)

Sodium form cation exchange softening and chloride form anion exchange dealkalization.

C

Raw Water Conductivity–(0.72 µS/cm/mg/L) X (mg/L HCO3 Removed) (c)

Weak acid cation or strong acid cation exchange/decarbonation and finally sodium-form cation exchange softening, dealkalizing.

D

≤ 0.2 X Raw Water Conductivity

Sodium-form cation exchange softening and first-pass RO.

E

≤ 0.01 X Raw Water Conductivity or ≤ 10 µS/cm

Sodium-form cation exchanger followed by two-pass RO or a twobed strong-acid cation followed by a strong-base anion exchanger.

F

≤ 1.0 µS/cm

Typically, RO followed by strong-acid and strong-base anion exchangers.

G

≤ 0.1 µS/cm

Typically, two-pass RO with nonregenerable mixed-bed or EDI (d), or with mixed-bed strong-acid cation/strong-base anion exchange demineralizer.

High purity

Ultrapure water

Notes: a) Sodium form cation exchange softening is commonly called sodium zeolite softening. b) The factor ranges from 0.52 to 0.53 as HCO3 and is 0.635 to 0.645 if bicarbonate alkalinity is expressed as CaCO3. c) The factor ranges from 0.715 to 0.729 microsiemens per centimeter per milligram per liter (µS/cm/mg/L) as HCO3. d) = electrodeionization

Table D: Hydroxide Production From Softened and Partially Dealkalized Water Drum Pressure (psig)

Conversion of Total Alkalinity to [OH] Alkalinity (%)

5

8

15

10

50

33

100

63

150

79

≥ 200

90

Interpolate percentages at other pressures. For example, the percentage breakdown of natural alkalinity to hydroxide or caustic alkalinity at a steam operating pressure of 125 psig would be as follows (using the coordinates in the table): %TA = [OH] = 63% + {[(125-100)/(150-100)] X (79-63)} = 71% So, with 10% makeup and 50 mg/L of TA in the softened makeup there will be 50 mg/L X 0.1 X 0.71 = 3.55 mg/L of OH alkalinity as CaCO3 generated in the steam generator per feedwater cycle maintained. At design maximum continuous blowdown (i.e., 5%), we would have 20 cycles (i.e., 100/5) of feedwater and a final drum hydroxide alkalinity of 71 mg/L as CaCO3. If the boiler water [OH]/[TA] alkalinity ratios were less than 0.71, then there is ghost hardness ingression into the feedwater. If it is greater than 0.71, then supplemental caustic or sodium is being added to the feedwater (i.e., ion exchange sodium leakage) or ingression into the condensate from a process leak. Conversions: As NaOH → as CaCO3, multiply by 1.25 As CaCO3 → as NaOH, multiply by 0.80

26 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

Steam Condensate System

Minimizing corrosion in the steam supply and condensate return system will reduce the amount of potential porous metallic-based (i.e., iron and copper alloys) deposition within the steam generator. It will also reduce the potential for heat exchange surface failures, leading to process side or cooling water in-leakage contamination and deposit formation within the steam generator. While departure from nucleic boiling can cause porous deposit formation, in its absence, internal chemical treatment additives are required to aid in avoidance of deposit formation. This then decreases the potential for wick boiling and underdeposit corrosion, with the final outcome being tube failures. Figure 4 shows a steam condensate/steam distribution system.

continued

Ammonia (NH3) will cause SCC of copper and copper alloys. The concentration needs to be controlled to avoid this; otherwise, the source of ammonia or unstable organonitrogen needs to be eliminated or the metallurgy changed. Couple DO2 with NH3, and even low levels of ammonia will chelate with cuprous oxide and remove it from the surface; thus, it will not be available to be oxidized into cupric oxide in the production of the protective cuprous/cupric oxide blend, thus thinning copper/copper alloy. See Table E. The solubilized copper in the preceding can then enter into redox reactions of other metal surfaces, primarily iron, thus causing galvanic corrosion to said surfaces in the feedwater system and boiler. Hot caustic attack from boiler water carryover or attemperator injection water associated with demineralizer regeneration failure will lead to SCC of carbon steel and stainless-steel piping, valves, and trim materials.

Figure 4: Steam condensate/steam distribution system.

Chemical corrosion inhibitors used in steamcondensate system include the following: • There are many forms of chemical and physio-mechanical corrosion that can occur in steam systems, as outlined below.

Chemically induced corrosion causes: Dissolved oxygen (DO2) results in pitting. Occurrence is typically associated with a branch of the steamcondensate system going down and drawing a vacuum. Carbon dioxide (CO2) will form carbonic acid upon steam condensing to water. Acids cause thinning of metal surfaces. Couple DO2 with CO2, and the acidic carbonic acid forms metal bicarbonates-carbonates that can be re-released by the DO2 in the formation of metal oxides and secondarily cause carbonic acid corrosion (i.e., thinning) downstream.

Neutralizing volatile amines (see Table F) are used to counteract carbonic acid attack and raise the pH up to 9.0 or from 9.4 to 9.6 if all ferrous (this also counteracts flow accelerated corrosion (FAC). There are many to choose from, but typically a blend of two or more are used to allow for systems of varying operating pressure and long run distances from the steam generation point. They are typically added to the feedwater after condensate polishing and thermal deaeration. They have feed rates that are proportional to the CO2 content of the steam. In high-carbon-dioxide-potential systems, the use cost of neutralizing amines may be too high, so a blend of them with a filming amine, or just filming amine, may be applied. Otherwise, a capital investment will be needed to install dealkalizing pretreatment equipment.

27 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

•

Filming amines (See Table G), in some cases termed as film-forming substances (FFS), are used and fed to the steam line or a branch line ahead of where a high corrosion-prone area exists. A stainless steel inject quill is always used. These amine’s requirements are not proportional to the CO2 in the steam, but rather to the mass steam flow supplied after the surface demand of the piping network is completed. They are fed at a rate of 0.25 to 3.0 mg/L active. Their films, once fully in place, will last up to two weeks, and subsequent feed is to maintain an excess only. That is, if an excess of 0.25 mg/L is required, when the values drop below 0.25 mg/L in the condensate, more is fed, and the feed may be for a few hours per day to once per week, empirically determined. The diamines used today—Noleyl-1,3-propylene Diamine (C21H44N2)—use about 0.25 parts per million (ppm) feedrates and provide better performance then octadecylamine (C18H37 NH 2 , ODA). This is due to the second amine group, propylamine, in which the nitrogen hydrogen bonds with the neighboring diamine’s octadecyl group, closing the gap between them, while still orientated 90 degrees to the surface like an ODA film.

•

continued

Volatile oxygen scavengers (VOS) are also used, not so much for their oxygen scavenging, but their ability to build protective oxide films faster than the presence of oxygen alone. This provides improved protection during a pH or FAC upset and permit reduced metals pickup in the condensate system.

Table E: Ammonia Concentration Acceptance in the Presence of Dissolved Oxygen Dissolved Oxygen (µg/L)

Ammonia Allowed (µg/L)

0–20

500

20–50

300

>50

Any level may be a problem

Table F: Commonly Used Neutralizing Volatile Amines Amine

Boiling Point °F

2 Amino-2 methyl-1 Propanol (AMP)

329

Ammonia

Formula

Molecular Weight

D.R1

C4H11NO

89

0.31

NH3 (NH OH)

35

10.0

Benzylamine

365 (211)

C 7H 9 N

107

3.5

Cyclohexylamine

274 (206)2

C6H13N

99

4.0

Diethylaminoethanol

325 (210)

C6H15NO

117

1.7

2

2

Dimethyamine

46

C 2H 7 N

45

11.4

Diethylamine

133

C4H11N

73

7.6

Dimethylaminoethanol

273

C4H11NO

89

1.3

Hexylamine

270

C6H15N

101

2.0

Methoxypropylamine

272

C4H11NO

89

1.0

Morpholine

262

C4H9NO

87

0.4

Carbon Dioxide

CO2

44

12

Monoethanolamine

C2H7NO

61

0

Notes: 1 D.R. = Distribution Ratio = Amount in the vapor / amount in the liquid 2 Azeotropic boiling point

28 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

continued

Table G: Commonly Used Filming Amines Filming Amine

Formula

Type of Amine

Hexadecylamine

C16H35NH2

Primary

Octadecylamine (ODA)

C18H37NH2

Primary

N-oleyl-1,3-propylene Diamine (FFS)

C21H44N2

Secondary

Dioctadecylamine

(C18H37 )2NH

Secondary

Bis(2-hydroxyethyl) Cocamine

C16H25NO2

Tertiary

Bis(2-hydroxyethyl) Oleylamine

C22H48NO2

Tertiary

1-ethyl amino 2-octadecylimidazoline

C23H45N2NH2

Tertiary

Physically induced corrosion causes:

Erosion corrosion (EC), excessive velocity of steam or condensate, strictly a line diameter size issue.

Water hammer due to condensate holdup (poor drainage), undersized line diameter, or carryover of boiler water, resulting in line fractures and displacement. Steam collapse, resulting in multiple undercut pits that have a deep base, and the side walls and base reveal very jagged surfaces similar to ice-picking. This morphology should never be confused with oxygen pitting, corrosion fatigue, or stress assisted corrosion (SAC). Subcooling of the condensate greater than 30 °F below saturation. Cavitation of pumps and control valves. Two-phase, flow-based FAC (surface looks like tiger stripes), calculate the correct line size needed for the two phases (condensate and flashed steam) to remove water droplet impingement or change metallurgy from 0.25 to 0.5% chromium or go from 304 to 316 stainless steel, depending on process side chemistry.

Poor condensate drainage, high condensate hold-up associated with improper valve sizing and control, steam supply pressure, condensate line back pressure, steam trap selection issue. Mechanical resolve by proper sizing of (See Table H for design velocities) (19) the following: • Steam lines. • Condensate lines. • Nozzles on containment vessels. • Condensate and steam control valves. • Steam traps and design type. • Single back pressure condensate systems with no higher-pressure orphan discharge into the system. Avoids steam stall due to effective drainage. • Venting of pressurized condensate pots and flash over drums.

Table H: Operational Design Velocities for Steam Generation and Transporting Transporting

Feet per minute (fpm)

Feet per second (ft/sec)

High-Pressure Steam

8,000–12,000

133.3–200

Low-Pressure Steam

12,000–15,000

200–250

Steam Under Vacuum

20,000–40,000

333.3–666.6

Superheater

2,000–5,000

33.3–83.3

Economizer

150–300

2.5–5.0

Steam Generator Water

70–700

1.17–11.7

Liquid Condensate

180–360

3–6

Flash Steam Condensate

6,000–12,000

100–200

29 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

continued

Unfortunately, there is no chemical solution to physically promote corrosion other than to engineer it out or upgrade the materials of construction. It is the former approach, if possible, that will prevail with time. More information regarding the theory, chemistry, and corrosion prevention in steam and condensate systems can be found in Reference 20. Mechanically and chemically caused corrosion identification, calculated corrective actions, and validation of the corrective actions as well as steam/condensate operational control can be found in Reference 21.

others may be present. Under these operating conditions, the increase in non-condensables will increase the partial pressure within the deaerator, reducing or restricting the amount of DO2 and CO2 that can be stripped and vented from the feedwater being processed. Increasing venting rates will be required until the excess contaminants are dispelled and the DO2 residual returns to baseline values. Additional information associated with testing feedwater DO2, deaeration operational designs, performance expectations, and performance trouble shooting can be found in References 22 and 23.

Feedwater/Economizer System

It is important to remove DO2 in the feedwater to avoid pitting in feedwater heaters and economizers. Although ferrous metallurgy in the feedwater can handle DO2 levels just below that of saturation temperature (i.e., oxygenated treatments and controlled low level oxygen presence), the same is not true for copper and copper alloys. The latter requires pH to not exceed 9.2 and oxygen to be nondetectable (i.e., - 300 millivolts oxidation reduction potential [mV ORP]). The same will hold true for the avoidance of internal corrosion if chelants are in used for hardness and metallic deposition control or ammonia is present in high quantities (Table E).

Boiler feedwater will contain condensed steam returns containing any corrosion products and process-side in-leakage that it may have picked up, plus the pretreated makeup water to replace steam losses and blowdown purges. If there is no condensate polishing being performed, then the first preconditioning step of the feedwater is preheating to remove the non-condensable corrosive and heat transfer insulating gases. Preheating also reduces thermal shock of the boiler metals, reducing the potential for corrosion fatigue and stress assisted corrosion. It also improves the capacity of the steam generator to handle accelerating process run-up loads, thus avoiding operating pressure reductions, steam stalls and departure from nucleate boiling. If the steam generating system is not equipped with a deaerator, then preheating the feedwater tank with direct live steam injection is performed to greater than 180 °F and ideally 200 °F if the NPSH (net positive suction head) required for the feedwater pump can be met. Preheating the feedwater tank will lower the DO2 to 1 mg/L and lower sulfite consumption. At the same time, it will reduce sulfate in the TDS and/ or the conductivity readings in low-pressure boilers. These changes can reduce the blowdown rates and the consumption of treatment chemicals, water, and fuel. Steam-operated deaerators have operating pressure that may range from 5 to 50 psig and are atmospherically vented to remove all the non-condensable gases stripped by this process. DO2 levels of less than 10 µg/L are expected. Care must be taken when the condensate becomes contaminated, as additional non-condensables such as volatile organic carbon, nitrogen, hydrogen sulfide, sulfur oxides (SOx), nitrogen oxide (NOx), and

Oxygen scavengers, metal passivators, and volatile oxygen scavengers chemically remove low levels of oxygen (i.e., polish) and produce reduced protective metal films such as magnetite (Fe3O4) and cuprous oxide (Cu 2O). They are typically fed to the feedwater via a sparger type injection line in the storage section of the deaerator or feedwater tank. In some high-pressure applications, they are fed to the high-pressure feedwater heater condensate crossover/flashover to the low-pressure feedwater heater. While sulfite is not a metal passivator, the conversion to the protective reduced oxides occurs naturally at 428 °F for iron (Schikorr Reaction) and 248 °F for copper, while the use of passivators lowers the temperature required and speeds up the film production, with less dependency on interferences associated with species with cation conductivity (i.e., chlorides and sulfates). The typical passivators used today are fed at five times stoichiometry of the DO2 in the feedwater plus a boiler water residual. In the low-pressure ranges, they are fed at 150 to 250 µg/L and then reduced for medium pressure, and then further reduced for high-pressure applications. The residuals

30 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

continued

maintained will depend on the operating pressure of the steam generator and the thermal stability of the passivator. An example is provided in Table I (24), whereby sulfite is the boiler water residual and hydrazine is the feedwater residual. The other passivators and VOS materials follow the hydrazine feed trend. The default for feedwater excess concentration for the newer passivators and VOS’s would appear to be 50 µg/L at 2,000 psig and 25 µg/L at 2,800 psig. It is known that sulfite begins to break down at 488 °F in 600-psig boilers to sulfur dioxide and hydrogen sulfide, both of which are corrosive. Therefore, for boilers with pressures above 900 psig, the newer passivators should be used instead of sulfite. In fact, these newer passivation technologies should be considered above 600 psig operating pressure or operate the at 5 to 10 mg/L sodium sulfite. Application data for some of the commonly used oxygen scavengers and metal passivators are provided in Table J (25). Table I: Recommended Oxygen Scavenger Residuals Operating Pressure Range (psig)

Sodium Sulfite (mg/L)

Hydrazine (mg/L)

0–150

30–60

0.1–0.3

150–300

30–40

0.1–0.3

300–600

20–30

0.1–0.2

600–900

10–15

0.05–0.1

900–1,200

5–10

0.02–0.05

1,200–1,500

3–7

0.01–0.02

Above 1,500

Use Hydrazine

0.01

Note: Sodium sulfite is residual in the boiler water and hydrazine is residual in the feedwater.

Table J: Application Data of the Various Oxygen Scavengers Available Scavenger

Dosage ppm/ppm O2

Direct Metal Passivation

Desired pH Range

Desired Temp °F Range

Volatility 1 D.R

Scavenger Rate Constant K2 (M -1 Min-1) Efficacy2

Sulfite

7.9

No

8.5–10

RT–540

0

1 X 104

Cat Sulfite

7.9

No

8.5–10

RT–540

0

1 X105

Cat HZ

1.0

Yes

9.5–12

200–400

0.023

3 X 10

HQ

3.43

Yes

7.5–11

N/A

0

3 X 103

CHZ

1.43

Yes

9.5–12

200–400

0.023

3 X 102

EA

5.5

Yes

8.0–11

185–622

0

2 X 102

DEHA

2.78

Yes

8.5–12

RT–422

1.26

2 X 102

MEKO

5.44

Yes

6.0–10

RT–572

9.8

5 X 103

Morpholine

n.a.

Yes

0.47

DEAE

n.a.

No

4.28

CycloHA

n.a.

No

28.5

4

Notes: 1) Distribution ratio (i.e., steam phase/water phase; DR) is at atmospheric pressure, and 212 °F zero valued compounds are not considered to be VOSs. 2) Efficacy is given in per mole per minute at pH 7.7 and 230 °F. 3) There are catalysts available for all scavengers. 4) Has 1,000 °F superheat survivability.

A word of caution: an increase in iron across an economizer may be due to corrosion fatigue (CF, pits associated with oxide filled cracks), SAC (deep undercut pits), or FAC (single phase flow has a surface that looks like an alligator hide). Check for steaming, increase the pH to 9.4 to 9.6, and see if the effluent iron levels decrease. It is too easy to dismiss the iron increase due to polymeric dispersant corrosion as these high-performance polymers will sequester and disperse 31 the ANALYST Volume 28 Number 4

Part 1: What Are Important Chemical and Pretreatment Programs for Industrial, Commercial, and Institutional Steam Generators?

iron very well. Should more information regarding passivation reactions, scavenger, passivators and VOS reactions, passivation strength and speed, typical application pH and temperature ranges, plus field results associated with metallics reduction and steam generator metallics recoveries (25).

Part 2

In Part 2 of this article series, we will take a look at the internal chemical treatment programs that are available. Some programs we will look at include All-Volatile Treatments, Oxygenated Treatment, Caustic Treatment, Phosphates, Polymers, Chelants, and Carbonate + Polymers.

References

1. ASME (1998). “Consensus on Operating Practices for the Control of Feedwater and Boiler Water Chemistry in Modern Industrial Boilers,” ISBN No. 0-7918-1204-9, American Society of Mechanical Engineers, New York, New York. 2. ASME (2006). “Consensus on Operating Practices for Sampling and Monitoring of Feedwater and Boiler Water Chemistry in Modern Industrial Boilers,” ISBN No. 0-7918-0248-5, American Society of Mechanical Engineers, New York, New York.

16. ASTM International (n.d.). “Standard Test Method for Sodium,” ASTM D-2791, ASTM Vol. 11.01, American Society for Testing and Materials, West Conshohocken, Pennsylvania, www.astm.org. 17. ASTM International (n.d.). “Standard Test Method for Silica,” ASTM D-859, ASTM Vol. 11.01, American Society for Testing and Materials, West Conshohocken, Pennsylvania, www.astm.org.

18. ASTM International (n.d.). “Standard Test Method for Degassed Cation Conductivity,” ASTM D-4519,” ASTM Vol. 11.01, American Society for Testing and Materials International, West Conshohocken, Pennsylvania, www.astm.org. 19. Combustion Engineering (1981). “Combustion Fossil Power Systems,” Combustion Engineering, p. 5-25, ISNB 0-960 5974.

20. Beardwood, E.S. (Feb. 19-20, 1991). “Steam Condensate Corrosion; The Mass and Energy Transfer Problem,” Section 9 of Practical Boiler Water Treatment, Technical University of Nova Scotia (TUNS; later to become EPIC, Educational Programs Innovation Center), Toronto, Ontario, Canada, additional information available at www.epictraining.ca. 21. Beardwood, E.S. (Nov. 3-5, 1997). “Operational Steam Condensate Corrosion Control of Reboilers and Reheaters,” Paper No. IWC 97-25, International Water Conference, Pittsburgh, Pennsylvania. 22. Beardwood, E.S. (April 17-21, 1989). “Boiler Feedwater Monitoring Applied to Deaerator Efficiency Improvement,” NACE International (now AMPP, www.ampp.org), Corrosion ’89, Paper No. 313, New Orleans, Louisiana.

23. Beardwood, E.S. (Nov. 6-10, 2016). “Feedwater and Deaeration within Industrial Steam Generating Systems,” Paper No. IWC-16-54, International Water Conference, San Antonio, Texas. 24. Dyer, D.F.; Hall, D.M.; Maples, G. (1979). Water Manual for Boiler Operations, 1st ed., Boiler Efficiency Institute, Auburn, Alabama.

3. ASME (2012). “Consensus on Operating Practices for the Control of Water and Steam Chemistry in Combined Cycle— Cogeneration Power Plants,” ISBN No. 878-07918-5998-8, American Society of Mechanical Engineers, New York, New York.

4. ASME (2017). “Consensus on Pre-Commissioning Stages for Cogeneration and Combined-Cycle Power Plants,” ISBN No. 978-0-7918-6126-4, American Society of Mechanical Engineers, New York, New York. 5. ABMA (2005). “Boiler Water Requirements and Associated Steam Quality for Industrial/Commercial and Institutional Boilers,” American Boiler Manufacturers Association, Vienna, Virginia.

6. TAPPI (2005). “Water Quality and Monitoring Requirements for Paper Mill Boilers Operating with Softened Water Make-Up,” TIP 0416-14, Technical Association of the Pulp and Paper Industry, Atlanta, Georgia. 7. TAPPI (2005). “Water Quality and Monitory Requirements for Paper Mill Boilers Operating with High Purity Feedwater,” TIP 0416-03, Technical Association of the Pulp and Paper Industry, Atlanta, Georgia.

8. British Standard (1997). “Recommendations for Treatment of Water for Steam Boilers and Water Heaters,” BS 2486: ISBN 0 580 26220 0. 9. EPRI (n.d.). “Comprehensive Cycle Chemistry Guidelines for Fossil Plants,” EPRI 1021767, Electric Power Research Institute, Palo Alto, California, www.epri.com.

10. IAPWS (n.d.). International Association for the Properties of Water and Steam, www.iapws.org. 11. 1VGB Power Tech Service GmbH, VGB-S010-(2011). “Guidelines for Boiler Feedwater and Steam of Steam Generators with Permissible Operating Pressure > 68 bar,” www.vgb.org.

12. Beardwood, E.S. (Oct. 26-30, 2008). “Silica in Steam Generating System,” Paper No. IWC-08-12, International Water Conference, San Antonio, Texas. 13. Beardwood, E.S. (Nov. 17-20, 2014). “Steam Purity in Heat Recovery Steam Generators,” Paper No. IWC-14-28, International Water Conference, San Antonio, Texas.

14. ASTM International (n.d.). “Standard Practices for Sampling Steam,” ASTM D-1066, ASTM Vol. 11.01, American Society for Testing and Materials, West Conshohocken, Pennsylvania, www.astm.org.

continued

15. ASTM International (2008). “Steam and Water Sampling, Conditioning and Analysis in the Power Cycle,” PTC-19-11 Performance Test Code, American Society for Testing and Materials, West Conshohocken, Pennsylvania, ISBN-13: 907-0-7918-3131-1, www.asme.org.

25. Beardwood, E.S. ( July 14-16, 2015). “MEKO–A Controlled Oxygen Passivation Treatment,” Electric Power Research Institute, 11th International Conference on Cycle Chemistry in Fossil and Combined-Cycle Plants with Heat Recovery Steam Generators, St. Louis, Missouri.

Edward S. (Ted) Beardwood is the founder of BC&T Inc. (Beardwood Consulting & Technologies Inc.) and has more than 43 years of experience in water treatment. Before starting BC&T, his career included technical and sales positions with major specialty chemical companies, including serving as the senior global applications consultant for Solenis LLC, technical director for the Canadian operations of the Ashland Water Technologies Division, and sales representative and area sales manager for the Dearborn Division of WR Grace (now Betz/GE/Suez). His experience in the industrial water conditioning industry includes full-service sales, sales management, new construction and commissioning of thermal systems, laboratory management, regulatory compliance, product management, R&D, and consulting. Mr. Beardwood is a past chair of Water Technologies and the Research and Technology Committee for Water and Steam in Thermal Systems for the American Society of Mechanical Engineers (ASME), as well as a former working member of Performance Test Code for High Purity Water Systems (PTC–31) and past chair of NACE International Research Committee STG 11 on Water (now Association for Materials Protection and Performance, SC 18 Committee). He may be contacted at edbeardwood@bctinc.org.

32 the ANALYST Volume 28 Number 4

Can a New Type of Tagged Polymer Replace Inert Tracers and Provide Accurate Monitoring of Antiscalant and Dispersancy Treatments? Klin Rodrigues, Ph.D., and Jan Sanders, Nouryon Surface Chemistry

34 the ANALYST Volume 28 Number 4

Abstract

Inert tracers, including pyrenetetrasulfonic acid sodium salt (PTSA), are used in water treatment applications to monitor the amount of formulation dosed into the system. Contrary to their intended purpose, these tracers do not accurately reflect the rate of consumption of active ingredients such as scale-inhibiting polymers in the system. A new line of tagged polymers (patents pending) has been developed by incorporating a fluorescent monomer moiety into the polymer backbone. This allows accurate in-line detection of “free polymer,” an indication of the amount of polymer in the system that has not been used up in mechanisms such as scale control and dispersancy. The ability to detect free polymer levels allows water treaters to minimize polymer costs by ensuring that the polymer is not overdosed. These novel polymers can be detected using fluorescent probes currently used to detect PTSA, meaning that no additional equipment investment is required. Adopting the innovative technology involves only replacing PTSA and non-tagged polymer with tagged polymer. Most importantly, the technology provides unprecedented monitoring and control for water treaters.

Background

Inert tracers such as PTSA (1, 2) and fluorescein (typically used in boiler feedwater) are used by the AWT community to monitor the dosing of formulations into water treatment systems. While inert tracers can help water treaters to monitor how much formulation is being added and maintained in their systems, these tracers do not indicate how much polymer is being consumed. Different components in the formulation are depleted at different rates, and the use of an inert tracer does not provide an accurate picture of how much active polymer is available to provide scale control and dispersancy in the system. Note: A dispersing treatment is used to keep water contaminants suspended so that they cannot form sludges and scales in the system. Tagged polymers contain a fluorescent monomer that is covalently bound to the polymer and can accurately indicate the amount of free polymer in the 1 to 50 parts per million (ppm) range. Therefore, consumption of the

polymer in the water treatment system can be measured. It is important to measure consumption of the polymer (3) directly since fluctuations in conditions such as water chemistry and temperature can result in a need for additional scale inhibiting/dispersant polymer to be added to the system. Most importantly, as the potential to form scale increases, the measured polymer concentration decreases, and therefore, the polymer concentration is an indirect measure or estimate of the scaling potential or stress in the system. Since the polymer concentration is being measured in real time, the operator can increase polymer concentration as needed to prevent scale. These tagged polymers can be monitored by using the same in-line fluorometer currently used to monitor PTSA, and so no additional capital investment is required. This article will discuss tagged polymers for carbonate and phosphate scale. “Tagged Polymer C” indicates a polyacrylic-acid-based tagged polymer for carbonate scale. Likewise, “Tagged Polymer P” is a tagged acrylic acid-AMPS copolymer for phosphate scale control. Both polymers are produced by a special process to maximize their scale inhibition properties. The polymer in a water treatment system exists in one of two states: as “free polymer” in the bulk solution that is not currently interacting with scale or the process of scale formation, or as a “used polymer,” which is polymer chains that are instantaneously interacting with scale particles and are engaged in minimizing scale formation. The amount of polymer contained in the water treatment system is the sum of the free polymer and used polymer. For each system, a scale boundary (3) exists beyond which the polymer is no longer effective for scale control. As polymer in a water treatment system is used up by mechanisms such as scale control and dispersancy, the fluorescent signal decreases. The measured amount of tagged polymer can be used in combination with other measurements, such as conductivity, to provide a more accurate view of the scaling environment and monitoring of increasing stress on the system. Without the benefit of accurate polymer detection, the water treater often will take a conservative

“The amount of polymer contained in the water treatment system is the sum of the free polymer and used polymer.” 35 the ANALYST Volume 28 Number 4

Can a New Type of Tagged Polymer Replace Inert Tracers

continued

approach to stay away from the system scale boundary, leading to both a large overdose of polymer and an inability to operate at higher cycles of concentration.

Detection: Calibration and Linearity

A typical fluorescence signal of a tagged polymer is depicted in Figure 1. Emission and excitation wavelengths are indicated on the x- and y-axes, respectively, where color indicates signal strength (ranging from blue-low to red-high). Figure 1: 3-dimensional fluorescent signal as measured by a Shimadzu RF 6000 Spectro Fluorophotometer.

In Figure 1, two local maxima are observed. Although the strongest signals are obtained at these maxima, the tagged polymer system has been designed to take advantage of existing fluorometers used to detect PTSA. Fluorometer 1 has excitation and emission wavelengths of 365 and 410 nanometers (nm), respectively (4), and Fluorometer 2 has excitation and emission wavelengths of 365 and 405 nm, respectively (5). Since the emission wavelength (410 nm) for Fluorometer 1 is closer to the emission wavelength of the local maxima (425 nm), a stronger signal is typically obtained with Fluorometer 1 than Fluorometer 2, as shown in Figures 2a and 2b. Figure 2a (left): Calibration curve for Fluorometer 1; Figure 2b (right): Calibration curve for Fluorometer 2.

Figure 2 demonstrates the ability to detect 1 to 15 parts per million (ppm) of Tagged Polymer C using Fluorometer 1 and Fluorometer 2, which are typically used to detect PTSA. These meters can be calibrated using different PTSA standards, typically 100 parts per billion (ppb) or 30 ppb PTSA. For purposes of detecting these tagged polymers, calibration with 30 ppb PTSA is preferred to obtain higher signal intensities (compare orange to black lines in Figure 2a and 2b). This enables the user to better detect and differentiate between low levels (1 to 2 ppm) of polymer, which are typical in certain applications, such as reverse osmosis feed streams. Regardless of the calibration used, one will 36 the ANALYST Volume 28 Number 4

Can a New Type of Tagged Polymer Replace Inert Tracers

continued

notice that the curves are extremely linear and the R2 is in the 0.98 to 0.99 range, which gives a reliable determination of the free polymer. Note: R 2 (R-squared) is a goodness-of-fit measure for linear regression models. This statistic indicates the variance in the dependent variable that the independent variables explain collectively. R-squared measures the strength of the relationship between the model and the dependent variable on a convenient 0 to 1 scale with numbers higher than 0.98 meaning an extremely good fit. Smart tagging and detection of stress on the system and free polymer. In water treatment systems, the scaling stress can increase for both phosphate and carbonate scale as water is recycled and higher cycles of concentration are achieved. As the carbonate scaling tendency or Langelier scaling index (LSI) of the system increases, the carbonate inhibition performance of a typical carbonate inhibition polymer decreases, as illustrated in Figure 3. Figure 3: Illustration of % carbonate inhibition versus LSI.

be measured. The water treater can then determine an appropriate set point for free polymer to ensure that the polymer dosage is sufficient to minimize or eliminate scaling. In addition, the polymer does not need to be grossly overdosed, resulting in economic and environmental benefits.

Phosphate Scale Control

A standard phosphate test was conducted using different levels (12.5, 15, 17.5, and 20 ppm) of phosphate inhibitor Tagged Polymer P at various levels (5, 7.5, and 10 ppm) of orthophosphate. The test conditions are listed in Table A. The free polymer is measured at the end of the test on unfiltered samples using Fluorometer 1, simulating in-line measurement of the polymer in the field. Table A: Calcium Phosphate Static Test Conditions Calcium Phosphate Static Test Conditions Ca

200 mg/L as CaCO3 (120 mg/L as Ca)

Fe

2 ppm

orthophosphate

5, 7.5, or 10 ppm

pH

8.7–8.9

Temperature

70 °C

Time elapsed

17 hours

Figure 4: Percent calcium phosphate inhibition and free polymer levels (measured by Fluorometer 1) versus different levels of phosphate for 12.5 ppm polymer.

As illustrated in Figure 3, the polymer gives greater than 90% inhibition at an LSI of 2.5 or below. Above an LSI of 2.5, the polymer performance rapidly decreases. Therefore, in this hypothetical system, an LSI of 2.5 can be considered a critical limit for polymer performance, defined as the system scale boundary. For most water treaters, the system is a black box, and in a typical water treatment system, many operators will stop well short of the system scale boundary to avoid the sometimes-steep edge at which scale begins to form. Polymer is typically overdosed because operators cannot tell how much polymer is being used up and how much free polymer exists in the system. The use of tagged polymers overcomes the difficulties seen in a traditional system. By using an in-line fluorometer, the amount of free polymer in the system can

Figure 4 shows the percent phosphate inhibition on the left Y axis and ppm free polymer on the right Y axis. It

“The free polymer is measured at the end of the test on unfiltered samples using Fluorometer 1, simulating in-line measurement of the polymer in the field.”

37 the ANALYST Volume 28 Number 4

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should be noted as the phosphate level goes up at this relatively low level of polymer, the percent inhibition decreases. The amount of free polymer detected decreases with increasing phosphate, indicating that the polymer level is a direct measure of the scaling tendency of the system. As the scaling tendency increases, the amount of polymer used to combat the scale goes up, and therefore, the amount of polymer left in the bulk solution goes down. This polymer left in the bulk solution is termed as “free polymer,” and this concept is analogous to chlorine used as a biocide. As it is important to measure the free chlorine to make sure that there is enough chlorine in the system to deliver the needed biocidal properties, the level of free polymer should be maintained such that there is sufficient polymer to inhibit scale.

Not surprisingly, the phosphate inhibition for this data point was very low.

At 12.5 ppm polymer, 90% inhibition is only obtained in the system with lowest phosphate level (5 ppm), and the free polymer level is 5 ppm. At 7.5 and 10 ppm phosphate, 90% inhibition is not achieved, and the free polymer level is 3.9 and 3.8 ppm, respectively. These data indicate that at least 5 to 7 ppm free polymer is necessary for inhibition under these conditions.

In the next test (Figure 6), the polymer level was increased to 17.5 ppm. Once again, the free polymer decreased with increasing phosphate levels. At 5 and 7.5 ppm phosphate, a 17.5 ppm polymer dosage was sufficient for 90% inhibition. The free polymer at 5 and 7.5 ppm phosphate was 7.7 and 6.9 ppm, respectively. This is above the 5-ppm free polymer, which was found to be the minimum level of free polymer in the previous two tests. At 10 ppm phosphate, the percent phosphate inhibition was 83%. Ideally, the phosphate inhibition needs to be 90% or greater. The free polymer was found to be 6.5 ppm. This indicates that under the most stressed conditions of this test (10 ppm phosphate), the minimum free polymer needs to be higher than 6.5. It is important to note that the minimum free polymer level needs to be designed for the most stressed system that would be encountered (10 ppm phosphate in these data sets).

Figure 5: Percent calcium phosphate inhibition and free polymer levels (measured by Fluorometer 1) versus different levels of phosphate for 15 ppm polymer.

Figure 6: Percent calcium phosphate inhibition and free polymer levels (measured by Fluorometer 1) versus different levels of phosphate for 17.5 ppm polymer.

Figure 7: Percent calcium phosphate inhibition and free-polymer levels (measured by Fluorometer 1) versus different levels of phosphate for 20 ppm polymer.

In the next test (Figure 5), the polymer level was increased to 15 ppm. Once again, the free polymer decreased with increasing phosphate levels. At 5 and 7.5 ppm phosphate, a 15-ppm polymer dosage was sufficient for 90% inhibition. The free polymer at 5 and 7.5 ppm phosphate was 6.2 and 5.2 ppm, respectively. This is above the 5-ppm free polymer, which was found to be the minimum level of free polymer in the previous test (Figure 4). More importantly, at 10 ppm phosphate, the free polymer was found to be 4.3 ppm, which is below the level of minimum free polymer required (5 ppm). 38 the ANALYST Volume 28 Number 4

Can a New Type of Tagged Polymer Replace Inert Tracers

continued

With 20 ppm active polymer (Figure 7), phosphate inhibition is more than 90% at all levels. More importantly, the amount of free polymer detected in the samples is between 7.5 and higher (8.2 and 8.8), which is above the minimum requirement for free polymer determined in the previous tests. In a real-life system, the free polymer level set point would probably need to be in the 8 to 15+ ppm range, depending on the particular system. If the system has a history of severe fluctuations in phosphate levels or a large number of hot spots, then the set point needs to be on the higher end. The higher the set point, the more insurance is built into the system. As more experience is gained with this tagged polymer system and different individual systems in the field, an estimated starting set point would be better defined and could be set as low as possible to minimize polymer usage. When the free polymer is below the minimum freepolymer level for phosphate, it means scale is being formed. At this point, the water treater should quickly add additional polymer or begin the blowdown process. A polymer reading that is below minimum free polymer level indicates that the system stress is greater than

polymer performance. A reading above the minimum free polymer level means that the polymer and formulation are in control of the system stress, and scaling is not occurring. The free polymer level acts as a polymer bank in the system (Figure 8a). During scale inhibition, polymer chains adsorb onto nuclei or surfaces of growing crystallites (Figure 8b) to prevent further growth. These nuclei or crystallites then redissolve or otherwise have their growth patterns altered, and the polymer chains are returned to the bulk solution (Figure 8c). As a result, polymers perform scale inhibition at substoichiometric levels. This dynamic equilibrium (Figure 8c) between free polymer and used polymer (i.e., polymer that is tied up in scale control and the process of crystallites forming, polymer adsorption and then redissolution) is maintained as long as the free-polymer level is above the minimum free-polymer level or until the system scale boundary is reached. It is important to note that the fluorescent signal only measures free polymer in the solution. Polymer fractions that are adsorbed onto crystallite surfaces (inhibition) or other particles such as dirt (dispersion) are not measured, likely because the individual polymer chains are not in a dilute solution matrix.

Figure 8: 8a (left), crystallites being formed, free polymer present; 8b (center), part of the free polymer used to adsorb onto the surface of the crystallite and combat scale; 8c (right), crystallite dissolving and polymer going back to the bulk of the solution as free polymer.

a

b

⇌

c

Scale control is maintained as long as the free polymer is above a certain minimum free-polymer level. However, if the scaling tendency increases and the system scale boundary is crossed, the number of crystallites ⇌ increases substantially (Figure 9a). As a result, there are more crystallites than polymer chains (Figure 9b) and the polymer is overwhelmed. The free-polymer level starts to drop below the minimum free polymer required to prevent scaling. As a result, the crystallites keep growing and scale is formed (Figure 9c). Figure 9: 9a (left), crystallites being formed, free polymer present; 9b (center), all of the free polymer used to adsorb onto the surface of the crystallite and combat scale; 9c (right), crystallite growing and forming scale.

a

b 39 the ANALYST Volume 28 Number 4

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Can a New Type of Tagged Polymer Replace Inert Tracers

continued

Carbonate Scale Control

Carbonate inhibition data for a series of LSI conditions using 10 ppm active Tagged Polymer C were generated using the test conditions detailed in Table B. These carbonate inhibition data are detailed in Figure 10.

Figure 11: Percent carbonate inhibition and free polymer levels (measured by Fluorometer 1) versus LSI for 12.5 ppm polymer.

Table B: Calcium Carbonate Static Test Conditions Variable

Static Conditions at 2.55 LSI

Ca

300 mg/L as CaCO3 (120 mg/L as Ca)

Mg

147.6 mg/L Mg as CaCO3 (36 mg/L as Mg)

Bicarbonate

350 mg/L as CaCO3 (427 mg/L as HCO3-)

Carbonate

80 mg/L as CaCO3 (48 mg/L as CO3-2)

pH

8.7–8.9

Temperature

50 °C

Time elapsed

17 hours

Figure 10: Percent carbonate inhibition and free polymer levels (measured by Fluorometer 1) versus LSI for 10 ppm polymer.

It is desirable to maintain at least 90% carbonate inhibition in these tests. These data in Figure 10 indicate that 10 ppm of Tagged Polymer C provides good inhibition up to an LSI of 2.6. At an LSI of greater than 2.6, carbonate inhibition drops below 90%. Therefore, the system scale boundary for this polymer under these conditions occurs at an LSI of 2.6 to 2.65. The free polymer measured in the LSI 2.0 to 2.6 range is 6 ppm. However, when the system scale boundary is exceeded (LSI >2.65), the free polymer starts to drop to less than 6 ppm.

“It is important to note that the absolute amount of free polymer is not as important as the detection of a decrease in free polymer.”

Figure 11 indicates that 90% inhibition is obtained up to an LSI of 2.65 when using 12.5 ppm of Tagged Polymer C. More importantly, the free polymer starts to drop at an LSI of greater than 2.65. Figure 12: Percent carbonate inhibition and free polymer levels (measured by Fluorometer 1) versus LSI for 15 ppm polymer.

Figure 12 indicates that 90% inhibition is obtained up to an LSI of 2.7 when using 15 ppm of Tagged Polymer C. As with lower polymer dosages, the free polymer starts to drop at the system scaling boundary (in this case, at an LSI of greater than 2.7). Also, as the polymer increases from 10 to 12.5 to 15 ppm (Figures 10 through 12), the free polymer level increases as one would expect. It is important to note that the absolute amount of free polymer is not as important as the detection of a decrease in free polymer, as indicated by lower fluorescence signal, which is observed at the system scale boundary. As long as the free polymer is maintained above a predetermined set point, 90% carbonate inhibition is achieved. This gives operators more flexibility to decide how close to the system scale boundary they want to get to before blowdown is recommended. This ability to go to higher

42 the ANALYST Volume 28 Number 4

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Can a New Type of Tagged Polymer Replace Inert Tracers

continued

cycles of concentration minimizes water utilization and maximizes cost savings. In addition, Tagged Polymer C provides scale protection (60 to 70% inhibition) in conditions just beyond the system scale boundary. This acts as an insurance policy, allowing the operator more time to respond with additional polymer dosing without having severe scale develop. This is not seen in the phosphate inhibition tests where the phosphate inhibition drops rapidly to unacceptable levels once the system scale boundary is passed (Figures 10–12). For both phosphate and carbonate scale control, the set point for the free polymer needs to be determined by experience with each individual system (makeup water and system scaling boundary). If the system has a lot of fluctuations then the set point needs to be high enough to account for the worst of the fluctuations, Whereas, if the system has minimum number of fluctuations, the set point can be lower. Furthermore, a higher set point is recommended for each system at the outset of the formulation change to the tagged polymer system. After monitoring the system for some time, the set point may be lowered, especially in systems with minimal fluctuations. Many water treatment systems have areas at which the potential for scale formation is increased. The temperature at heat exchange surfaces, in particular, can cause areas where scaling may be occurring, even when current monitoring of bulk water parameters such as conductivity may not indicate the existence of scale in these areas. A higher dosage of polymer may be required to combat scale formation in areas of high-scaling potential, resulting in less free polymer being detected in the bulk water. This decreased free-polymer level will trigger the operator or the automated controller to pump additional polymer into the system to maintain scale control. In this way, the tagged polymer system can better account for hot spots and other disturbances in the system that are not addressed by current monitoring strategies.

Formulations

Most current water treatment formulations contain a polymer for phosphate scale control that also acts as a dispersant. In addition, formulations may contain a polymer such as polymaleic acid (PMA) for carbonate scale control as well as an inert tracer such as PTSA.

The suggested formulation changes are relatively simple. First, the PTSA needs to be removed from the formulation. If the formulation is designed for phosphate scale control, Tagged Polymer P needs to replace the phosphate scale-control polymer in the formulation on an equivalent polymer activity basis. If the formulation is designed for carbonate scale control, Tagged Polymer C needs to replace the carbonate scale control polymer so that PMA is in the formulation on an equal polymer activity basis or even at a lower concentration. Tagged Polymer C is a much better calcium carbonate scale control agent than PMA and therefore, the calcium carbonate performance of the formulation will be enhanced if it replaces PMA in the formulation at an equal level. Detailed formulations including the use of Tagged Polymer P to replace both untagged polymers in the formulation are provided in the follow-up paper (6). This technology can be used in a conventional one-drum formulation. However, the utilization of the technology can be maximized if a two-drum formulation could be employed, in which the polymer is fed separately from the rest of the formulation. In this manner, the polymer utilization is minimized, and the maximum cost savings would be obtained.

Conclusions

Inert tracers, such as PTSA, are used in water treatment applications to monitor the amount of the formulation in the system. These tracers do not reflect the amount of active ingredients, such as scale-inhibiting polymers, at equilibrium conditions. Tagged polymers (6–8) have been developed by incorporating a series of fluorescent monomer moieties into the polymer backbone. This allows accurate in-line detection of “free polymer,” an indication of the amount of polymer in the system that has not been used up in mechanisms such as scale control and dispersancy. These tagged polymers are compatible in systems with stabilized bromine or hypochlorite as the oxidizing biocide. The ability to detect free polymer allows water treaters to minimize polymer costs by ensuring that the polymer is not overdosed. These novel polymers can be detected using fluorescent probes currently used to detect PTSA, meaning investment in additional equipment is unnecessary. The formulation change is relatively simple and

44 the ANALYST Volume 28 Number 4

Can a New Type of Tagged Polymer Replace Inert Tracers

continued

only requires replacing PTSA and a non-tagged polymer with tagged polymer. In addition, the technology allows for detecting the scaling stress of a system, which allows water treaters to go to higher cycles of concentration while using free-polymer levels to avoid crossing the system scale boundary. It could help minimize the number of trips that field personnel must make to check on the system, which has become more important in the current pandemic environment. The technology provides unprecedented monitoring and control, saves money, and minimizes water use. Additional information, such as tagged polymer stability in the presence of oxidizing biocides on two different types of tagged polymers, has been recently published. Field studies (8, 9) on these two different types of tagged polymers are also now available.

Acknowledgments

The authors would like to thank the following individuals for their contributions to this technical article: Mr. Jobie Jones for polymer synthesis, Mr. Steve Leuty for applications testing, and Mr. Dan Ghere for analytical data.

References

1. Hoots, J.E.; Hunt, B.E. (Nov. 8, 1988). “Fluorescent Tracers—Chemical Treatment Monitors,” U.S. Patent No. 4,783,314, accessible at www.uspto. gov.

Klin Rodrigues, Ph.D,, is a principal scientist in the Polymer Product Chemistry Group at Nouryon. He has been with Alco Chemical/AkzoNobel/Nouryon for more than 26 years. Dr. Rodrigues has authored over 30 technical papers and holds more than 75 U.S. patents. He holds a Ph.D. in polymer science and a master’s degree in chemical engineering from the University of Akron. He earned his bachelor’s degree in chemical engineering from the Indian Institute of Technology Bombay (India). Dr. Rodrigues can be contacted at klin.rodrigues@nouryon.com. Jan Sanders is a senior researcher with Nouryon. She has a bachelor’s degree in chemistry from the University of Tennessee at Chattanooga and has worked in various roles for Nouryon and its predecessors over the past 23 years. Ms. Sanders has experience with design and synthesis of polymers and their use in water treatment and oilfield applications. She has five granted patents and has co-authored several technical publications. Ms. Sanders can be reached at jannifer.sanders@ nouryon.com. This article is based on a presentation given at the AWT 2020 Interactive Annual Convention & Exposition, which was conducted September 29– October 2, 2020.

2. Moriarty, B.E.; Hickey, J.J.; Hoy W.H.; Hoots; J.E.; Johnson, D.A. (Feb. 12, 1991). “Continuous On-Stream Monitoring of Cooling Tower Water,” U.S. Patent No. 4,992,380, accessible at www.uspto.gov. 3. Schaefer, W.P.; Pilsits, J.P. (May 2004). “On-Line Systems Aid Cooling System Chemistry Control,” Water Technology, accessible at www. watertechonline.com/process-water/article/16210493/online-systems-aid-cooling-system-chemistry-control. 4. Pyxis Lab (n.d.). “SP-350 PTSA Handheld Meter,” website product information, Pyxis Lab Inc., Lafayette, Colorado, accessible at https:// pyxis-lab.com/product/sp-350/.

5. Turner Designs (n.d.) “Opti-Check Handheld Fluorometer,” website product information, Turner Designs Inc., San Jose, California, accessible at https://www.turnerdesigns.com/opti-check-handheld-fluorometer. 6. Rodrigues, K.A.; Sanders, J. (Sept. 23-25, 2021). “Fluorescent Tagged Polymers in Water Treatment Applications,” AWT 2021 Annual Convention & Exposition, Providence, Rhode Island, Association of Water Technologies, Rockville, Maryland.

7. Rodrigues, K.A.; Bailey, A.J.; Jones, J.L.; Winkenwerder, W.A.; Band, E.I. ( July 2018). “Water Soluble Pyranine Polymers and Method of Making,” Patent No. WO 2019025305A1. 8. Rodrigues, K.A.; (December 2020) “Method of Controlling Scale in Aqueous Systems,” Patent No. WO 2020/243176A1.

9. Blackmore, T. (Sept. 23-25, 2021). “Field Trials and Observations of Tagged Polymers,” AWT 2021 Annual Convention & Exposition, Providence, Rhode Island, Association of Water Technologies, Rockville, Maryland.

45 the ANALYST Volume 28 Number 4

How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process Swati Sharma, Ph.D., Water Engineering Inc.

46 the ANALYST Volume 28 Number 4

Sunflower oil refinery wastewater produces large quantities of fatty-acid-rich wastewater with a high concentration of organic pollutants (1). Sunflower oil wastewater is typically treated by dissolved air flotation (DAF) and chemical coagulation followed by anaerobic digestion (2–4). Over time, the efficiency of the DAF system is reduced due to a high influx of oily/fatty contents coming in at a large loading rate. As a result, the wastewater is either diverted from DAF to storage ponds or redirected to the anaerobic lagoons, thereby resulting in increased organic loads. These processes take up huge acres of land and potentially contribute to environmental issues (5, 6). Currently, electrochemical processes are being studied to find an alternative solution to these traditional treatment methods. These processes are an advanced technology that achieve a chemical reaction through generation of electricity. Electrochemical processes help minimize the use of chemicals, thereby preventing formation of byproducts. Of the various types of electrochemical processes, the most common is electrocoagulation (EC), which is found to be effective in removing small colloidal and suspended particles. On the other hand, advanced oxidation processes (AOPs), such as electro-oxidation (EO), electrofenton (EF), electroperoxidation (EP), and electrochemical peroxidation (ECP), have been effective in removing small organic compounds via oxidation. EC, when coupled with EO, has achieved better treatment of carwash, petroleum, tobacco, and olive oil processed wastewater. This study is focused on investigating the efficiency of EC+EO and ECP methods through optimum parameter conditions for maximum removal efficiency of total organic carbon (TOC), chemical oxygen demand (COD), dissolved organic carbon (DOC), and soluble COD (sCOD) in sunflower oil refinery wastewater.

Materials and Methods

The raw wastewater samples were collected from a local oil refinery in Fargo, North Dakota. The raw influent was analyzed for TOC, COD, DOC, and sCOD right after collection, and the wastewater was stored at 4 °C. The samples were discarded every three days and collected afresh. The unfiltered samples were analyzed for TOC and COD. The samples were then filtered through 1.2 -micron (µm) glass microfiber filter paper followed by 0.45-µm pore size filter paper to determine initial parameters in the

sample. The pollutants passing through the 0.45-µm filter were considered to be soluble components. About 50 milliliter (mL) of raw sample was filtered and used to determine initial concentrations of sCOD and DOC. The sCOD was analyzed using Hach testing kits TNT 821 and 822 (COD 0-150 milligrams per liter [mg/L] and 2-1500 mg/L, respectively). The DOC was analyzed using a Shimadzu TOC-L analyzer. The EC+EO and ECF processes were carried out simultaneously. The combined EC+EO process was performed in two phases: Phase 1: EC using aluminum electrodes as anode and cathode. Phase 2: EO process using boron doped diamond (BDD) electrode as anode and stainless steel as cathode. On the other hand, the ECF process was carried out using iron electrodes. Hydrogen peroxide (H2O2) was added externally at a dosage of 3 mL per 250 mL of sample (7, 8). The conductivity and pH were adjusted using sodium chloride (NaCl) and acid/base, respectively. The samples were collected from the reactors at regular intervals and analyzed for organic concentration.

Statistical Analysis

Box Behnken Design (BBD) was considered as the expermental design for evaluating the operating conditions at optimum conditions. The statistical analysis and modeling was performed using Design-Expert® software where the independent variables under consideration are pH/H 2O2 dosage, current density, and time. Three different levels were selected for each variable based on preliminary experimental study.

Results and Discussion TOC, COD, sCOD and DOC Removal in EC+EO Process In the EC process, the coagulation time decreased with an increase in current density. Using Al electrodes resulted in high removal of particulate organic concentration within a short time, ranging between 90% and 93% at all current densities under study. It was observed from this current study as well as previous literature that the EC process is efficient in removing particulate organics compared to that of dissolved organic compounds. Thus, the EO process was combined with

47 the ANALYST Volume 28 Number 4

How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process

continued

the EC process for further removal of dissolved organic pollutants. Performing EO after EC for 7 hours (h) achieved removal of an additional 80% of the remaining EC effluent organic concentration. The data for the EC+EO were fitted to quadratic models, and the model significance was tested using ANOVA (Table A). The best treatment condition yield through response surface plotting shows that the optimal treatment efficiency in Phase 1 of the EC+EO process was at current density of 5.69 milliamps per square centimeter (mA/cm 2) when operated for 18 minutes (min) at a pH of 6.07. In these operating conditions, the removal achieved for TOC and COD was 90% and 73.7%, respectively. For the EO process, the maximum removal of organic concentration was achieved at a pH of 5.27 and current density of 11.56 mA/cm 2 at the end of 400 min. The combined EC+EO process removed 95% of the raw influent organic concentration. From the response surface plotting presented in Figure 1, it can be inferred that the current density did not have significant impact on EC process; however, when EC+EO were combined, the effect of current density played an important role in achieving desired removal efficiency. Figure 1: Interaction effects of current density, pH, and time in the EC+EO process.

TOC, COD, sCOD, and DOC Removal in the ECP Process: The variables considered for the ECP process were H 2O2 dosage, current density, and time. The only difference in the selection of variables between EC+EO and ECP is choosing H 2O2 dosage over pH. This is due to the fact that Fenton’s Reaction is optimum at pH 2.8. Below or above this pH, Fenton’s Reaction produces undesirable intermediate reaction inhibitory complexes. Thus, the pH in this process was kept constant at 2.8. On the other hand, the H 2O2 dosage is critical in the formation of hydroxyl ions, which is the key redox exchange ion for the advanced oxidation process. At optimum operating conditions, which are achieved at an H 2O2 dosage of 14.2 mL/L and a current density of 7.56 mA/cm 2 for 278 min. The overall removal efficiency achieved using this process ranged between 81% and 85% of organic pollutants. The statistical significance was analyzed using BBD, and the model adequacy was tested using ANOVA, as presented in Table A. Figure 2 shows the interaction effects of time, current density, and H 2O2 dosage in the ECP process. It is 48 the ANALYST Volume 28 Number 4

How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process

continued

observed that H 2O2 dosage and time had a positive effect on the removal process. The results showed that an increase in current density decreases the time required to remove the organics. However, the percentage removal remains consistent at all current densities applied. The ECP process also yielded comparable results, and the removal was comparatively lower than that of EC+EO process. A previous study conducted by Sharma and Simsek (9) that investigated the effect of current density and time in the canola oil refinery wastewater using EC+EO and ECP processes achieved similar conclusions. It was observed that an increase in applied current density significantly decreases the time of operation maintaining a consistent removal. Figure 2: Interaction effects of current density, H2O2 dosage, and time in the ECP process.

Table A: ANOVA Results for the Quadratic Models for Sunflower Oil Wastewater Response (Y, %)

Source

EC+EO SS

DF

MS

F-value

p-value

SS

DF

MS

F-value

p-value

COD

Model Residual Lack of Fit Pure Error Total

376.50 5.23 4.56 0.6667 381.73 R²=0.9863 427.01 12.33 10.33 2.00 439.33 R²=0.9719 375.50 10.23 9.56 0.6667 385.73 R²=0.9735 289.93 7.00 6.33 0.6667 296.93 R²=0.9764

8 6 4 2 14

47.06 0.8718 1.14 0.3333

53.98

<0.0001

153.72 5.19 7.13 1.33

0.0003

0.2387

8 6 4 2 14

29.59

3.42

1229.77 31.17 28.50 2.67 1260.93 R²=0.9753 1424.57 27.17 24.50 2.67 1451.73 R²=0.9813 1074.00 33.73 31.73 2.00 1107.73 R²=0.9695 997.16 18.44 15.78 2.67 1015.60 R²=0.9818

5.34

0.1638

sCOD

Model Residual Lack of Fit Pure Error Total

TOC

Model Residual Lack of Fit Pure Error Total

DOC

Model Residual Lack of Fit Pure Error Total

ECP

7 7 5 2 14 7 7 5 2 14 7 7 5 2 14

Adj R²=0.9680 C.V%=1.03 61.00 34.64 <0.0001 1.76 2.07 2.07 0.3576 1.0000 Adj R²=0.9439 C.V.%=1.50 53.64 36.70 <0.0001 1.46 1.91 5.74 0.1550 0.3333 Adj R²= 0.947 C.V.%=1.36 41.42 41.42 <0.0001 1.000 1.27 3.80 0.2214 0.3333 Adj R²=0.9529 C.V.%=1.15

8 6 4 2 14 7 7 5 2 14 8 6 4 2 14

Adj R²=0.9423 C.V.%=2.93 178.07 39.33 0.0001 4.53 6.13 4.59 0.1867 1.33 Adj R²=0.9563 C.V.%=2.82 153.43 31.84 <0.0001 4.82 6.35 6.35 0.1417 1.0000 Adj R²=0.9391 C.V.%=3.03 124.64 40.55 0.0001 3.07 3.94 2.96 0.2683 1.33 Adj R²=0.9576 C.V.%=2.45

49 the ANALYST Volume 28 Number 4

How to Estimate the Best Treatment Conditions for Sunflower Oil Wastewater Using Advanced Electrooxidation Process

Conclusion

The sunflower oil wastewater was treated using two different electrochemical processes: combined EC+EO and ECP. The study showed that combining EC and EO resulted in higher organic removal. The removal efficiency had a significant dependence on current density, pH, and time. The performance of ECP was maximum at optimized operation conditions, and H 2O2 dosage impacted the organic removal concentration.

Acknowledgement

This research was funded by North Dakota Water Resource Research Institute and North Dakota Agricultural Experimental Station. The author would like to thank Water Engineering Inc. for providing the opportunity to present this study at the 2020 AWT Virtual Conference.

continued

Swati Sharma, Ph.D., completed her doctorate in environmental engineering from North Dakota State University, specializing in wastewater treatment and quality monitoring. Dr. Sharma has six years of experience in industrial, municipal, and agricultural water/wastewater treatment using biological, physicochemical, and electrochemical methods. Currently working as wastewater technical consultant at Water Engineering Inc., Dr. Sharma is involved with in-house analytical laboratory management, chemical formulations, and technical consulting in industrial water and wastewater solutions. She may be contacted at ssharma@ h2oeng.com.

References

1. Aslan, S.; Alyuez, B.; Bozkurt, Z.; Bakaoglu, M. (2009). “Characterization and Biological Treatability of Edible Oil Wastewaters,” Polish Journal of Environmental Studies 18(4), pp. 533-538.

2. Decloux, M.; Lameloise, M.L.; Brocard, A.; Bisson, E.; Parmentier, M.; Spiraers, A. (2007). “Treatment of Acidic Wastewater Arising from the Refining of Vegetable Oil by Crossflow Microfiltration at very Low Transmembrane Pressure,” Process Biochemistry 42(4), pp. 693-699.Uniphos 2020.pdf 3. Mkhize, S.; Atkinson, B.; Bux, F. (2000). “Evaluation of a Laboratory-Scale Biological Process for the Treatment of Edible Oil Effluent,” Water SA 26(4), pp. 555-558.

1 4/23/2020 3:57:49 PM

Uniphos

4. Rajkumar, K.; Muthukumar, M.; Sivakumar, R. (2010). “Novel Approach for the Treatment and Recycle of Wastewater from Soya Edible Oil Refinery Industry—an Economic Perspective,” Resources, Conservation and Recycling 54(10), pp. 52-758.

5. Azbar, N.; Yonar, T. (2004). “Comparative Evaluation of a Laboratory and Full-Scale Treatment Alternatives for the Vegetable Oil Refining Industry Wastewater (VORW),” Process C Biochemistry 39(7), pp. 869-875. 6. Seres, Z.; Maravic, N.; Takaci, A.; Nikolic, I.; M Soronja-Simovic, D.; Jokic, A.; Hodur. C. (2016). Y “Treatment of Vegetable Oil Refinery Wastewater Using Alumina Ceramic Membrane: Optimiza-CM tion Using Response Surface Methodology,” Journal of Cleaner Production, 112, pp. 3132-3137.MY 7. Sharma, S.; Simsek, H. (2020a). "Sugar Beet CY Industry Process Wastewater Treatment Using Electrochemical Methods and Optimization ofCMY Parameters Using Response Surface MethodolK ogy,” Chemosphere, 238, p. 124669. 8. Sharma, S.; Ahmet, A.; Halis, S. (2020b). “Electrochemical Treatment of Sunflower Oil Refinery Wastewater and Optimization of the Parameters Using Response Surface Methodology,” Chemosphere, 126511.

9. Sharma, S.; Simsek, H. (2019). “Treatment of Canola-Oil Refinery Effluent Using Electrochemical Methods: A Comparison Between Combined Electrocoagulation plus Electrooxidation and Electrochemical Peroxidation Methods.” Chemosphere, 221, pp. 630-639.

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Have you ever been stuck in the field with a question? Reluctant to call someone about something you should know? The AWT Troubleshooting Guides are the resource you’ve been looking for.

The current supply chain crisis is having a major impact on our industry. We have added upcoming webinars and articles to our website intended to help AWT members navigate this crisis. To access this information visit https://www.awt.org/members-section/supply-chain-resources/.

Available guides include: Troubleshooting Algae in a Cooling System Troubleshooting Flow Switch Troubleshooting High Bacteria Counts in Cooling Towers To view the guides, visit https://www.awt.org/ members-section/troubleshooting-guides

52 the ANALYST Volume 28 Number 4

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Industry Notes AMSA, Inc. Names Janice Shawl New President

H2O

AMSA, Inc., chemical manufacturer of BCP™ series (DTEA II™ base chemistry), announces the promotion of Janice Shawl to president.

In the words of founder, CEO, and CTO Attila Relenyi, “Promoting Janice to the office of president is a key step to AMSA’s succession and its growth strategy to allow me to concentrate on the launch of AMSA R&D Corporation, focused on novel chemistries. Janice Shawl has a comprehensive grasp of the operations of AMSA as well as on the science upon which AMSA’s unique technology is based.” Janice Shawl is a co-founder and primary investor in AMSA. During the foundational years of AMSA, Janice built dual careers: one at AMSA and the other as an administrator in the Special Education Department at Midland Public Schools. She gained valuable experience completing business missions in China, Taiwan, and the Philippines to develop key international accounts. Upon ending her career in the school system, she was able to devote her energies full time to AMSA since 2011, serving as vice president and director of marketing and sales. University training and education has served Janice and AMSA well. She earned a B.A. in education from Michigan State University and an M.A. in teaching reading and language arts from Oakland University. In reflecting on her new position, Janice states, “As AMSA celebrates its 25th year in business, it is exciting to lead AMSA and build upon its track record of bringing innovative chemistry to the water treatment industry. It is an awesome responsibility to run AMSA, which has always prided itself as a technology company manufacturing products focused on an ‘all-in-one molecule’ rather than ‘chemical blends.’” Janice resides in Midland, Michigan, and Sandy, Utah. For more information, visit www.amsainc.com.

Pam Simmons Joins Watson Marlow

Watson Marlow Fluid Technology Group (WMFTG) is pleased to announce the addition of Pam Simmons as district sales manager to its Process 2 4 Industries Division, Industrial OEM sales team. Pam comes to Watson Marlow with more than 20 years in the industrial water treatment sector. Her passion, knowledge, and vast experience will assist WMFTG in further developing its Process Industries OEM business.

H SO

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Larry Gottlieb and Frank DeSilva Honored by WQA

A pair of ResinTech veterans were honored with WQA Leadership Awards for their commitment to the water treatment industry at this year's WQA Convention & Expo in Las Vegas. Frank DeSilva and Larry Gottlieb were recognized with the 2021 "Key" and “Ray Cross” Awards (respectively).

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Industry Notes continued

Jeffrey Gottlieb, ResinTech’s CEO, said, "This recognition by WQA is well-deserved and highlights the energy both Larry and Frank have put toward the WQA and to advancing the interests of our industry—that's always been part of our culture at ResinTech. My dad (ResinTech founder Michael Gottlieb) always encouraged us to engage with various organizations and with our colleagues from around the industry. Larry and Frank's example and mentorship will hopefully inspire the next generation of water treatment industry leaders."

Key Award Like receiving the key to a city, this WQA member is recognized for demonstrating the highest qualities of leadership within his/her company, industry, and various associations, as well as in local civic and community activities. Francis J. (“Frank”) DeSilva is national sales manager for ResinTech Inc., where he has worked for more than 30 years. He holds an M.S. in environmental engineering from New Jersey Institute of Technology and has authored numerous articles on ion exchange and related topics. Frank serves on the board of directors of the Pacific Water Quality Association and is a past president of that association. He is also a member of the AWWA Ion Exchange Standards Committee and serves on the Legislative and Regulatory Committee of AWT. He is a longtime WQA member and serves as chair of the Federal Government Relations Committee.

Ray Cross Award In honor of Ray E. Cross, water specialist emeritus and past president of Water Conditioning Association International in 1960, this special award recognizes a current or former WQA member whose pioneer spirit and unwavering commitment has made a notable difference in the water treatment industry and who has not been previously honored with the Hall of Fame or Lifetime Member Award. Larry Gottlieb has been president since 2017 of ResinTech, Inc., a company his family started. During his tenure, he launched several subsidiary businesses, including Aries Filterworks and ACM Technologies. Larry earned a degree in mechanical engineering from

the University of Pittsburgh and began his career with Holtec International, a leader in the nuclear power field. He serves on the WQA board of directors and is a member of the U.S. Department of Commerce’s Environmental Technology and Trade Advisory Committee. He also supports the Jewish Federation of Southern New Jersey, particularly in its efforts providing housing, assisted living, and long-term care for the elderly. For more information, visit www.resintech.com.

Solugen Announces Expansion of Its BioforgeTM Technology Platform

Solugen, the company decarbonizing the chemicals industry, has recently announced a Series C financing round of over $350 million. The latest round of funding will be used to expand Solugen's BioforgeTM technology platform, which is used to produce lowercarbon and carbon-negative chemicals and materials for its key customers, and to expand the reach of Solugen's product portfolio. Solugen’s BioforgeTM is the world’s first carbon negative molecule factory. The 10,000 tons per year (tpy) plant produces green chemicals from biophased feedstocks and eliminates more than 30,000 tpy of CO2 equivalents.

Through its BioforgeTM platform, Solugen has the potential to address a significant portion of the chemical products on the market today as well as introduce novel, bioadvantaged products. The most recent fundraising round allows Solugen to continue expanding the footprint of the BioforgeTM technology to give industries the products they need to reduce emissions in their existing supply chains without compromising on performance or economics. The company’s breakthroughs in enzyme and metal catalyst engineering allow them to produce chemicals in a more sustainable and profitable way. This, in return, delivers performance benefits, cost savings, and most importantly, lower carbon footprints to Solugen’s customers. To learn more about the company and its mission to decarbonize the chemicals industry, visit www.solugen.bio.

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Industry Notes continued

PWT and Genesys Become the H2O Innovation Specialty Chemicals Group, Expand Sales Force and Manufacturing Capacity

H2O Innovation Inc. (“H2O Innovation” or the “Corporation”) is proud to announce that its two specialty chemical business lines, PWT TM and Genesys®, came together on July 1, 2021, to form the H2O Innovation Specialty Chemicals Group. At the same time, the company will increase its sales force with the addition of new territory managers and expansion of manufacturing capacity in its Cheshire (UK) facility. While both entities will continue to exist in this new group, and there will be no changes to the current product portfolio, the new combined management structure will leverage the strengths of the leadership of Genesys and PWT. It has been 18 months since H2O Innovation completed the acquisition of Genesys International Ltd., with the goal of eventually creating, with PWT, a single specialty chemicals group with a common vision. Steve Chesters will lead this team as vice president and managing director, Ryan Furukawa will assume the role of vice president–Technology, Matt Armstrong will become vice president–Sales, and Mazen Ellabban will take on the position of global mining industry manager. “This new structure will bring the wealth of membrane knowledge that exists within both the PWT and Genesys sales, research, and manufacturing teams to all our customers. They will also have access to a wider range of chemical products and services. We are of course committed to respect agreements currently in place as we look for every opportunity to bring the synergy of the combined group to the market through our distribution network,” stated Frédéric Dugré, president and chief executive officer of H2O Innovation. The specialty chemicals team has long considered the benefits of local presence in high-potential regions, such as the Middle East and Asia. Starting July 1, 2021, Iqbal Ahmad will represent H2O Innovation in Southeast Asia. Iqbal has developed a tremendous level of expertise having worked extensively on significant projects across these regions in his long tenure in the water treatment industry. Currently based in New Zealand, he will be responsible for supporting growth of Genesys and PWT distributors, in part by continuing to implement the

corporate key account strategy. Further hires in North America as well as internationally are also expected by the end of the fiscal year. The company is also very excited to announce the expansion of operations in the Cheshire, UK, manufacturing facility. A project is underway that will nearly double the warehouse area, allowing the shop to manufacture PWT’s dendrimer-based antiscalant, which will continue to be manufactured in Vista, California. The project will also expand the capabilities of blending both Genesys and PWT powder products to better serve European and Asian customers, reduce shipping delays and freight costs, and improve gross profit by insourcing its manufacturing. “This project to expand our facility in the UK is a strategic move which reduces the risks associated with having a single point of manufacture for our dendrimer scale inhibitor. It will also allow us to be more competitive on the products we sell, to have better quality control, to enjoy better margins and to reduce our water footprint. We are working towards being able to manufacture all products from Genesys and PWT in either of our two locations. By manufacturing and blending the right products in the right location, we will optimize freight and tariff costs,” added Gregory Madden, chief strategy officer of H2O Innovation. For more information, visit www.h2oinnovation.com.

De Nora Completes One of the World’s Largest Produced Water Recycling Projects

De Nora, a global leader in the delivery of sustainable technologies, is pleased to announce the completion of phase one of its Delaware Basin Wastewater Recycling Project, achieving aspirational produced water rates exceeding 140,000 barrels per day – a total of more than 5 million barrels over a 30-day period. The highest quantity recorded in the company’s history, De Nora and its project partners set a new benchmark for the industry, charting the path to a more sustainable future in oil and gas production. “De Nora is leading the charge in produced water recycling,” said Alex Gonzalez, president of De Nora Neptune. “Understanding the various challenges we face as an industry and society as a whole, including water

56 the ANALYST Volume 28 Number 4

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scarcity and increased seismic activity, we prioritize providing our customers with ESG-friendly services that integrate seamlessly with existing operations. Our method enables the greenest, safest, and most efficient approach to produced water recycling for reuse into hydraulic fracturing.”

the UV Technologies Division from Calgon Carbon Corporation. The company’s portfolio of water treatment solutions leads the industry in addressing complex water challenges, including those faced in the oil and gas industry. For more information, visit www.denora.com.

The project, which began in May, established four ClorTec Mobile Treatment Units along a network of simultaneous fracturing systems. The modular setup, perfected by De Nora, gives producers the ability to target areas of concern at any point in the upstream or midstream water utilization cycle, tapping into existing pipelines or feeding directly off saltwater disposal wells. This reduces the reliance on freshwater for planned fracturing activity, while also eliminating the emissions traditionally required for the transport of water to the site—two major challenges faced in the energy sector.

Ecolab Inc. has entered into an agreement to acquire Purolite, a leading and fast-growing global provider of high-end ion exchange resins for the separation and purification of solutions, that is complementary to Ecoloab’s current offering and critical to safe, highquality drug production and biopharma product purification in the life sciences industries. Purolite also provides purification and separation solutions for critical industrial markets such as microelectronics, nuclear power, and food and beverage. The acquisition is valued at approximately $3.7 billion. Based in King of Prussia, Pennsylvania, Purolite operates in more than 30 countries and employs approximately 1,000 people worldwide, with expected 2021 sales of approximately $0.4 billion.

De Nora’s patented electrochlorination process is effective at killing bacteria populations without the use of hazardous chemicals, enhancing the safety for workers on site as well as for the surrounding environment and ecosystem. Solar salt, used in De Nora’s solution in place of complex chemicals, is sourced responsibly through renewable wind and solar processes and greatly reduces trailer traffic compared to chemicals and water transport, supporting the company’s commitment to offsetting carbon emissions without compromising cost or effectiveness. “Climate change continues to fuel severe drought conditions around the globe, which is especially evident in energy production regions. The industry is constantly evolving to do our part in reducing our carbon footprint and protecting water, our most precious resource,” commented consultant Brian Mueller of B2K4 Consulting. “The EPA estimates annual water usage for hydraulic fracking to be as high as 140 billion gallons. This project recently completed by De Nora Neptune and its partners proves that a drastic reduction in water supply use in this figure is achievable. In addition to the environmental impact of using dwindling freshwater supplies, there is also a steep economic cost; the technology used in the project provides both sustainability and financial benefits to the market and leaves freshwater supplies available for other community use.” Success in the Delaware Basin comes on the heels of De Nora’s acquisition of Grundfos’ ISIA S.p.A. and

Ecolab to Acquire Purolite

Purolite will operate as a separate global business unit and its overall results will be reported within Ecolab’s Life Sciences Division. Commenting on the transaction, Christophe Beck, Ecolab’s president and chief executive officer said, “With 2021 sales of $0.4 billion and mid-teens growth, Purolite is an acquisition that brings us a fast-growing leader in biopharma and industrial purification solutions with very strong margins. With this transaction, we will significantly increase our opportunities in our high growth, high margin life sciences business, such as the purification of mRNA vaccines and monoclonal antibodies for cancer-treatment drugs. By combining Ecolab’s stateof-the-art capabilities in clean and safe processing with Purolite’s revolutionary resin technology, we will provide a comprehensive and game-changing offering that will make the customer’s end-product better, safer, healthier and more effective. At the same time, it will further expand our capabilities in industries that are complementary to our already existing leading positions, such as the polishing of advanced microelectronics, ultra-purification of water in nuclear power, food and beverage taste and product quality enhancement, high-end precious metals extraction, like lithium for EV batteries, as well as in the production of hydrogen fuel cells.”

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Amplify AWT

YOUR VOICE HONORS OUR LEGACY.

AWT Members Engage in Year-Long Growth Conversation

During the AWT Annual Convention in Providence, Rhode Island, the AWT Governance Task Force presented the first Amplify AWT town hall. Focused on the future sustainability of the association and at the board’s direction, the task force spent much of the summer evaluating potential changes to the AWT bylaws that would address current growth obstacles and “Amplify” AWT into the future. The goal of this conversation over the next year is to engage the membership with proposed changes, answer questions, and conduct a transparent discussion on the future of the organization. The following is a summary of the information that was presented to the membership both at the convention and at a virtual town hall held this past October.

Why are we having this discussion?

1. Current bylaws are inhibiting growth that would lead to long-term sustainability.

5. If we continue to contract at this rate, AWT will have fewer than 450 companies by 2029.

2. Bylaw caps on annual revenue and employees were put into place to ensure that the largest companies were not eligible for membership. However, existing limits and categories are preventing growth and engagement.

6. The primary reasons we are losing members according to exit survey data:

3. A membership contraction is already leading to a decline in resources and talent and intellectual capital for all members, which is diluting the value of the organization. 4. The membership has contracted, on average, 3% each year since 2017.

a. M&A is resulting in fewer companies and in some cases (a loss of intellectual capital) less talent. b. Changes in the market. Of note, very few exit interviews show “lack of value” as a reason for not renewing.

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Amplify AWT continued

What are the two potential bylaw changes being discussed as part of Amplify? Increasing the Cap to 500 Employees or Fewer

Adding an Individual Member Category

Rationale. According to the SBA categorization for our type of business, a “small business” is 500 employees or fewer, so it would follow an existing precedent.

This category would be restricted from: 1. Voting in AWT elections.

With the cap set at 500 employees, we serve our historical desire to keep the big companies out of AWT and remain small business focused.

3. Chairing any AWT committee

It has been almost two decades since the size restriction has been modified, which has not allowed for inflation. By setting the increase higher than just the inflation rate, we can account for growth into the future. Members would not be punished/excluded for growing. Historically, excluding members who have grown has resulted in a loss of talent/intellectual capital/contributions for the good of the members. Members who have had to leave committee participation because their company sized out would be able to return. We would allow for growth and increase member engagement, all while still remaining true to the spirit of helping small business owners. Along with this change, the committee recommends restructuring the dues to more effectively reflect the benefits received relative to company size.

2. Sitting on the board of directors

4. Participating in any “business owner only” functions, including the business owners meeting website.

They would get: 1. Access to member educational resources. 2. Member pricing for all events. 3. Ability to participate in committees, but not chair. 4. Greater connection to our community, but no decision-making control.

Rationale & Benefit to AWT AWT small business owners would gain access to a wider network both domestically and abroad. New participants would enrich the value of the AWT community. There are many talented individuals who could contribute to the talent pool and thereby increase our collective intellectual capital. A new membership category would be available to AWT without giving anyone who works for a large company any power within the organization. Individual membership would help AWT gain a greater international footprint. Individual membership would only be conferred to those who do not qualify for membership via their company. Visit awt.org for more information.

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CWT Spotlight

Bart Ramplin, CWT Chemco Products Company Paramount, California

What prompted you to obtain your CWT, and when did you begin the process by taking the test? Like many others that are part of the AWT, I had spent my career working for large companies that do not participate or promote AWT. That changed when I made the decision in April 2021 to join Chemco.

How did you prepare for the test? I prepared for the test by reviewing the AWT Technical Reference and Training Manual and by taking the practice exam that the AWT provides on the website. The practice exam was especially helpful in my preparation because it gave me an idea of the types of questions to expect and the topics to spend more time learning.

At Chemco, I became more aware of AWT and the power of networking and idea sharing with my peers within the water treatment industry. I quickly saw the value in obtaining my CWT as a way of validating my credibility with customers and the next step in the evolution of my career. I began the process by taking my CWT exam in July 2021.

Why do you feel this credential was important to have? I feel this credential is important to have because it provides credibility and demonstrates professionalism.

What advice would you give those thinking about taking the exam? My advice for those that are thinking about taking the exam is to just do it. Prepare yourself by utilizing the resources that the AWT provides for exam preparation. I especially found the practice exam helpful.

What do you think are the most prominent issues facing the water industry today? I believe the most prominent issues facing the water industry today are sustainability, water and energy conservation, and water reuse. Our industry must continue to evolve by finding environmentally friendly and sustainable solutions for our customers. We play an integral role in helping our customers utilize resources effectively and efficiently.

While taking the exam, if there is a question that is not clear, skip it and come back. For me, many of the questions that had me stumped became clear to me after I gained some momentum and came back to them a second time.

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Making a Splash

Victoria Smith Water Engineering, Inc. Mead, Nebraska

What prompted you to start volunteering with AWT? I have been a member of AWT for three years. Water Engineering, Inc. extended the offer to join shortly after I signed on with their organization. It is a great benefit to be a part of the premier water treatment professional organization. Having said that, most people get busy with everyday work activities, and I fell into that habit, pushing AWT into a passive role. On a specific occasion where I needed research materials, I delved into the available materials on the website. It then occurred to me that I had an unbelievable opportunity to access up-todate materials, allowing me to excel in my research and account management. The opportunity to join a subcommittee was available. This was the perfect means for me to be active in AWT, keeping the access to current water treatment trends at the forefront of my to-do list! What has been the most rewarding thing about volunteering? I have been very blessed to have had excellent, qualified trainers and leaders in my past roles in manufacturing, quality assurance, and water treatment. I believe that it takes very small input from a seasoned professional to make a direct impact on water treaters early in their career. There comes a point in every professional’s career that we should look to see how our experience may benefit others. In the field of water treatment, where we cannot immediately see the impact of our treatment program, solid treatment advice is one of the only means to resolve issues due to the uniqueness of client systems. How has volunteering improved your professional career? I realized the impact of volunteering early in my water treatment career when my previous employer made judging science contests at local small school systems a priority. He is a P.E. and we, of course, were always busy. Placing a priority on children from elementary

to high school, it was clear to me that there was value to spreading awareness of STEM to rural areas. Additionally, as a woman in a technical field, I could see an obvious impact. It is rewarding to think that my experiences and approach to problem-solving may benefit our field of water treatment, ultimately improving our natural resources by providing efficient operations with a minimal impact on the environment. It is startingly clear that water treaters will become increasing important due to climate change and dwindling resources. I plan to continue to challenge myself to make volunteering a priority in my professional career.

Why would you encourage others to become a volunteer? The value of a professional organization such as AWT is only present if the content is applicable to current needs. The collective research, case studies, projects, and experiences create the powerful engine of AWT. Without input from real-time experiences, we will find that materials become outdated. Simply stated, if you would like to have a resource for water treatment, we must contribute to it.

Tell us about a current project you or your committee is working on. Semra Gul and I have partnered on a webinar series titled “A Series of Solutions.” The concept is loosely based on communicating by podcast. The technique has been quite effective at reaching a large and diverse audience throughout much of the pandemic. We chose to discuss basic cooling system concepts, to evolve into advanced concepts relating to methods of treatment, products of choice, usage rates, and techniques. It is meant to be a meeting place for discussion with seasoned professionals to assist with program choices.

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Making a Splash continued

What is a past project that your committee produced that you feel has had the greatest impact on AWT and why? I am new to the subcommittee! I place importance on technical papers concerning best practices. When developing a project for a client, inclusion of professional technical papers from AWT are an excellent tool for clear explanation of variables and consequences. How have you been able to utilize the expanded business connections you’ve made while volunteering? My employer, Water Engineering, Inc., has recently expanded to the East Coast. My exposure has been in the Midwest, West, and South. Meeting folks on the Cooling Subcommittee have opened my network to the eastern United States and Canada. Exceptionally qualified colleagues managing different source water and negotiating current market trends are a massive benefit!

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64 the ANALYST Volume 28 Number 4

C A N A D A

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Tales From the Waterside

Why Proper Operation of Boiler Pretreatment Equipment Matters By Gene Tonetti, Water Systems Management, LLC

The importance of properly operating boiler pretreatment equipment cannot be overstated. To overlook its operation can result in corrosion, deposition, and/or excessive chemical usage. A key piece of boiler pretreatment equipment is the deaerator. A deaerator is a pressurized vessel that can remove dissolved oxygen in the feedwater down to 7 parts per billion. The deaerator will also remove carbon dioxide and ammonia gases as long as the gases remain in nonionized molecular form.

Spray-Type Deaeration

Designs vary from manufacturer to manufacturer; however, the two most common designs are spray-type and tray-type deaerators. In the spray-type deaerator, boiler makeup water enters the primary preheater section through spring-loaded spray valves. The sprays break up the makeup water stream into smaller droplets that allow more water surface area to be exposed, thus increasing

steam/water contact and improving gas scrubbing efficiency. The low-pressure (typically 5 pounds per square inch gauge [psig]) steam enters the lower section of the vessel and flows upward through either channels or internal piping, depending on design. The deaerated water then drains into a larger tank called the storage section. It is here where the chemical oxygen scavenger is injected to react with the small amount of dissolved oxygen that remains in the mechanically deaerated water. Spray deaerators work well in applications where variations in flows are minor and when operated at or close to average design flow conditions. If there are wide steam flow swings or high variation in boiler steaming rates, they typically do not produce consistent low oxygen levels in the boiler feedwater. Figure 1 shows an example of a spray-type deaerator.

Figure 1: Diagram shows raw water, low-pressure steam, and condensate return entering the top side of the deaerator.

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Tales From the Waterside continued

Tray-Type Deaeration

Tray-type deaerators are similar in design, except that stacked stainless steel trays are installed under the spray valves. The preheated spray water flows downward over the trays forming a thin, uniform water film. These thin water films allow the dissolved oxygen to flow rapidly to the water surface, where the oxygen escapes into the vapor phase with the steam. Proper venting of the dissolved gases to atmosphere takes place in the high point of the deaerator steam dome. The tray-type deaerator is ideal for wide swings in boiler steam load or operation at low process steam demand conditions because of the ability of the tray stacks to better distribute and retain the falling water, which results in longer steam/water contact time than the spray-type unit.

the valve on the deaerator vent line to save the hospital money by eliminating the wasted steam that was venting to atmosphere! We explained that the vent line needed to remain open to allow the oxygen to be removed because it would otherwise enter the boilers and cause oxygen pitting corrosion. This explained why the boiler water sulfite readings were not increasing even though the hospital had tripled the chemical feed rate. At our direction, the boiler operator began to slowly open the vent valve while we observed the deaerator pressure and temperature gauges. As he opened the valve, the deaerator pressure began to decrease, and we had him adjust the vent valve until the pressure was at 5 psig. At that point, we observed that the temperature gauge was very close to 228 °F, which is what our steam tables said it should be.

Field Case Study #1

We advised the operators to leave the sulfite oxygen scavenger chemical pump at the same settings for the next 12 hours and call us in the morning after they had performed their morning water testing. The next morning, we received a call and found the boiler water sulfite reading had increased from 6 parts per million (ppm) to 83 ppm.

When we arrived at the site, I noticed no visible vapor leaving the ½-inch deaerator vent line as we walked toward the boiler room from the parking lot. The hospital personnel allowed us access to the rooftop, and we were able to confirm there was no vapor exiting the vent line.

The boiler personnel were happy that we were able to easily solve this problem, and as a result of this and other work previously performed by our sales engineer, we were able to obtain this new account that had been held by a competitor for more than 20 years.

We went to the boiler room and found that the spraytype deaerator was operating at 10 psig. However, the water temperature in the deaerator storage section was only 210 °F. At 10 psig, the water temperature should have been 240 °F.

In 1992, my company obtained a water treatment service contract at a Midwestern soybean crush plant. The crush plant produced soybean flakes and extracted soy oil from the beans.

Several years ago, a Midwestern hospital complained of a problem with low-oxygen scavenger (sulfite) levels in its boilers and the occurrence of pitting on some of the tubes that had not been present during previous boiler inspections. The hospital used the steam for heating hot domestic water and its hot water space heating loops.

Upon questioning the boiler operating personnel, one of the newer employees admitted that he had closed

“The hospital personnel allowed us access to the rooftop, and we were able to confirm there was no vapor exiting the vent line.”

Field Case Study #2

After several service visits, I found the deaerator was not functioning properly, as it was operating near 15 psig and the temperature was only 220 °F. At 15 psig, the feedwater temperature should have been 250 °F. In addition, the deaerator emergency pressure relief valve was set at 15 psig and frequently “popped off” several times a day. This became a real safety concern for the operating personnel, as the deaerator was frequently overpressurizing. I recommended an inspection of the deaerator during the upcoming plant shutdown.

67 the ANALYST Volume 28 Number 4

Tales From the Waterside continued

“Plant personnel have confidence and listen to people who can identify and solve problems that the plant may not have recognized previously.” The customer had a tray-type deaerator. When we inspected the tray section, we found that the trays were not in proper alignment, as they were unevenly stacked, apparently because they had been installed upside down! The plant engineer called the deaerator manufacturer and requested internal assembly drawings be faxed to the plant as soon as possible. We were then able to determine how to properly install the trays and quickly performed the correct installation. We also discovered that the steam flow regulator was defective, so it was replaced, thus eliminating the overpressurization problem. A few days after boiler startup, we noted that the deaerator pressure was now at 10 psig with the temperature at 238 °F, which was within 2 °F of design. Over the next few weeks, we began tracking boiler water sulfite usage to makeup water usage and found it to be less than it was prior to the boiler inspection.

Conclusions/Takeaways

One of the quickest ways to gain credibility in an account is to become a good analytical person. Plant personnel have confidence and listen to people who can identify and solve problems that the plant may not have recognized previously. A thorough understanding of how boiler pretreatment equipment works is essential and can distinguish you from a competitor. In both case studies, the previous service reps had held the water treatment business for several years and had not brought up the deaerator problems to the plant managers. Most likely, neither of these accounts would have changed suppliers if we had not discovered the problems and addressed them. Gene Tonetti is the founder of Water Systems Management. He has worked in the water treatment field for more than 41 years, and has expertise in wastewater, high-purity, boiler, and cooling tower water. His experience in treating water includes treatment chemicals, chlorine dioxide, reverse osmosis, and process controllers. Mr. Tonetti is a 1973 graduate of Rose-Hulman Institute of Technology with a B.S. in biological engineering. He is a CWT with AWT and can be reached at gtonetti73@gmail.com.

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Life Beyond Water

The Big 4: Misconceptions in Estate Planning Elizabeth A. Anderson, Esq., The Law Network, P.C.

In my estate planning practice here in the Denver Metro area, I am often asked to teach classes on estate planning to the community. I absolutely cherish these opportunities because not only do I get to help people navigate this difficult area of law, but I also help them avoid bad estate planning practices. Picture This… We have all been exposed to what I call the “barber’s special” when it comes to estate planning. You are sitting in the barber’s chair, getting your hair cut, and you hear the person next to you discuss the issues they are facing because a loved one died. Everyone chimes in with advice. Here are two examples: “When my mom passed away, we had to go to court to figure it all out.” “Court isn’t necessary. If they had a will, you are fine.” People are generally trying to be helpful, but it can create more confusion and, at times, costly mistakes. To help you get on the right track with your own estate planning needs and goals, I want to focus on the 4 biggest misconceptions in estate planning so that you can plan correctly.

Misconception 1: Estate Plans Are Just for the Wealthy

When we hear the term “estate,” we often imagine mansions and mega yachts, but the word simply means the assets that you own at the time of your passing. That could mean a home, a car, a bank account, maybe some retirement accounts or brokerage accounts.

“When we hear the term “estate,” we often imagine mansions and mega yachts, but the word simply means the assets that you own at the time of your passing.” Additionally, estate planning isn’t just about inheritance issues. A major component of estate planning is helping you maintain control during your lifetime. For instance, do you have documents in place that dictate your end-oflife care or what will happen if you become incapacitated? If not, have you at least legally directed someone to make those decisions for you? A solid estate plan can help ensure your wishes are carried out.

Misconception 2: I’m Not Old Enough to Worry About This I wish this were the case, but as soon as you turn 18, an estate plan becomes key. When we all woke up on our 18th birthday, we became adults and, with this, we became our own decision-makers. I’m not saying we were smart enough or mature enough to have this power, but legally, we were now in control of our own decision-making.

While we probably didn’t own any assets that necessitated having a will or trust at the age of 18, we probably should have had some basic estate planning documents to help us navigate financial and medical decisions. I know it isn’t a fun 18th birthday present, but make sure your adult children have a financial power of attorney (POA) and a medical POA.

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What Is a Financial Power of Attorney? A financial POA is a legal document that allows you to appoint a helper, called an “agent,” to manage your finances on your behalf. I think a lot of people take this document for granted, especially when married. Most people assume that if you are married, your spouse can manage your finances if you are in a hospital or nursing home, but that is not the case. If the asset is not jointly held with your spouse, your spouse has no legal authority to access it. For instance, your retirement accounts are not jointly owned. Those accounts are only accessible by you. You may also have separate bank accounts from your spouse. How are we going to access those individually held accounts if you become incapacitated? This also applies to any adult in your life. Your adult child probably has their own bank account. They might pay for their own cell phone or car. While our instincts say that, as their parent, we should have the authority to help them, legally that is not the case. When we don’t have this legal document in place, and a person lacks the capacity to execute a financial POA, a court will need to get involved. In Colorado, we call this court proceeding a “conservatorship.” In a conservatorship hearing, the judge determines whether someone needs to be appointed to manage your financial affairs. If the judge finds that a person is unable to manage their own finances, a court order is issued appointing someone to act as their conservator. Typically, a family member is appointed, but the court could instead appoint a professional to act in that capacity. Conservatorships are all abuzz right now because of the ongoing legal battle regarding pop singer Brittany Spears’ conservatorship. (Note: A California court closed the conservatorship in November 2021.) Not all

“A financial POA is a legal document that allows you to appoint a helper, called an “agent,” to manage your finances on your behalf.”

conservatorships are bad. They can be incredibly helpful for some families. Other times, they are excessive and an unnecessary expense. Personally, I like to avoid court proceedings whenever possible. Get a financial POA in place. It is inexpensive, you can avoid an expensive conservatorship court proceeding, and it keeps you in control.

What Is a Medical Power of Attorney? A medical POA is similar to a financial POA, but this document covers everything about your physical person. It covers not only medical decisions but also potential nursing home placements and end-of-life decisions. I had a client whose child was in a serious car accident. Their child turned 18 while he was in the hospital, and the parents’ authority to make medical decisions stopped on his birthday. The hospital looked to the parents initially to make emergency decisions, but once their child was stabilized and they had to make decisions regarding ongoing care, the hospital required the parents to get a court order to be their child’s legal decision-maker. In Colorado, that court process is called a “guardianship.” A guardianship is similar to a conservatorship, as I described previously, but instead of dealing with money and assets, the guardian deals with decisions regarding the physical person, such as medical decisions and care placements. Again, this could be a completely avoidable expense if we are proactive and have a valid medical POA in place.

Misconception 3: I Have a Will, So I’m All Set

A will is the tool by which we nominate the person who is going to settle an estate. This person used to be called the executor, but now we generally refer to them as a personal representative. The personal representative has the task of settling your estate and distributing the assets in the manner you designate in your will. Unfortunately, a will is not that simple. A will, at least in the state of Colorado, by itself, does not avoid probate. A will can be a perfect tool for many families, but we need to be smart as to how we use it. Before we delve into that, though, let me explain what probate is.

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What Is Probate? Probate is a legal proceeding in which a judge gives their blessing to the personal representative to retitle your assets. The problem with a will is that it doesn’t have retitling mechanisms built into it. This is why the courts have to get involved. In Colorado, if you own real estate or you have more than $70,000 in assets, you will have to go to probate, and the court will have to ensure your assets are being retitled to the correct people. Probate isn’t the end of the world, but we really like to avoid it when we can. With probate, your death is now on display, and you have less privacy when settling your estate. Creditor notices get published in newspapers. Your estate is part of a public record. On top of that, it normally takes a year to close a probate estate and, if real estate or complex assets are involved, it can take even longer. When an estate includes unpaid debt, the estate can be held up for years. Creditors also have the right to file a claim against the estate, and when this occurs, these debts may need to be paid or negotiated down when there are insufficient assets in the estate. Probate is also expensive. National figures estimate that a probate can normally cost somewhere between 2 to 5% of the estate’s total value. These expenses may include legal and court fees and associated costs (e.g., surety bonds).

How to Avoid Probate If you have a will, make sure it is legally sound and that you have the necessary tools to avoid probate. When I say “tools,” I really mean make sure your assets have retitling mechanisms. This can be easily done by naming beneficiaries on your assets. If you have life insurance or retirement accounts, did you set up your beneficiaries? Do you also have contingent, or backup, beneficiaries listed? Sometimes our assets or beneficiaries are more complex, though, and we may need to look at completing a trust.

“If you have a will, make sure it is legally sound and that you have the necessary tools to avoid probate.”

What Is a Trust? I like to imagine that a trust is like a bucket. This bucket catches all your assets when you pass away. Your trust document then dictates what we do with these assets and is managed by your successor trustee, a person that you name in that trust document. This can be a huge help when someone owns real estate or they have special concerns regarding their beneficiaries (i.e., minor children, special needs individuals), or we just want to create more control and structure regarding the distributions to our beneficiaries. Each attorney has their own method when creating trusts for their clients, but I like to individually draft trusts for each of my clients. This way, the trust can be specifically written to address your personal concerns and wishes. A trust can be drafted so that you designate not only who inherits but also when they can inherit and how they inherit. For instance, maybe you have concerns that your child will someday divorce. Your trust can be written in a way that your child’s inheritance will be divorce proof, bankruptcy proof, and creditor proof. Maybe you are concerned about long-term care costs. You could use a different type of trust to shield assets from Medicaid Long-Term Care asset limitations. This is why I find trusts so fascinating. The options in trust drafting can really be limitless. One of the best things about a trust is that it doesn’t require court intervention. There is no need for a probate. A trust has the retitling mechanisms that a will lacks. With a trust, your successor trustee has the authority to follow the rules you set forth in your trust document and is able to pass out the inheritance based on your designated wishes. No probate. No court. Trusts can be a great tool. They aren’t just for the ultrawealthy. Rather, trusts are used to avoid probate and direct the timing and use of those distributions.

Misconception 4: I Found Forms Online and Can Do This Myself

Even though we want to avoid probate, please be careful about attempting this on your own. I know those online legal sites and services are tempting because of their low-cost options, but you are taking a huge risk. When you fill in these documents on your own, there is a risk of completing them incorrectly or executing them without 71 the ANALYST Volume 28 Number 4

Life Beyond Water continued

the proper formalities, such as witnesses or a notary, or both. By the time you or your family find out that these documents are wrong, it is too late. You have passed away, and now your family must deal with an expensive legal process to figure it all out. Be careful with your estate plan because you really do get what you pay for.

Final Thoughts

Everyone has different goals when it comes to estate planning. Are you concerned about your own potential disability or incapacity? Do you want to avoid probate? Are you concerned about how your beneficiaries will manage the inheritance when you pass? Are you afraid of running out of money for your long-term care costs? These are all things that can be addressed in a properly drafted estate plan. If you do nothing, you or your family will go to court at some point That could mean a guardianship or conservatorship during your lifetime or a probate after your death. With estate planning, so much is personal and fact specific. It is also very state specific. Please seek the advice and guidance of a local estate planning attorney. Let them provide you peace of mind, not only for yourself but also your loved ones.

“Beyond Water…” is a new column for the Analyst that addresses issues that AWT members face in addition to their important work in the water treatment business. If you have an idea for an article, please feel free to send your suggestion to mdhenleywater@gmail.com. We welcome your input. Elizabeth A. Anderson, Esq., is an attorney specializing in estate planning, business planning, special needs planning, and elder law. She is a partner of The Law Network, P.C., a trusts, estates, and business planning law firm in Metro Denver. Ms. Anderson started her legal career working for the New York State Appellate Court. While there, she represented individuals with mental illness, intellectual and developmental disabilities, and the elderly in a variety of court proceedings, including guardianships and conservatorships. When she is not working or volunteering, she enjoys time with her husband and their two young sons. Her family loves adventure, and you will often find them hiking, skiing, or traveling. Ms. Anderson may be contacted at elizabeth@ coloradoestateplanners.com. ©2021, Elizabeth A. Anderson, The Law Network, P.C.

Disclaimer

The content of this article is based on the author’s personal experiences and professional training. It is not intended to be legal advice. Readers with questions should seek the advice of a licensed attorney to address their specific situation.

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T.U.T.O.R.

Technical Updates, Tips, or Reviews

Why Silica Matters Mike Henley, MD Henley & Associates

In the course of water treatment, the professional water treater will face many challenges. Some come from the treatment approach, but the bigger puzzle that must be solved comes from the local water quality, which is subject to biofouling, corrosion, fouling, and scaling in the process of using the treated water. Through all of this, one of the bigger challenges faced in some facilities comes from silica. Silica is considered to be the second most abundant material on earth after oxygen. Different forms of it are found in water, which makes it no surprise that its removal is a constant challenge in different treatment areas. This article will briefly examine some basic aspects of silica and its impact on some aspects of water treatment/usage. Please note that this article is not an in-depth look at silica but is meant to provide an initial overview about this important subject. For those who wish to delve deeper, the “Digging Deeper” section lists several resources for additional background.

Background

Silica comes from the element silicon and is a combination of one silicon atom and two oxygen atoms. It is also referred to as silicon dioxide (SiO2). Silica takes many forms and is found in rocks, sand, and materials such as silt and clay. For water treaters worldwide, silica can be a serious problem if not removed from the feedwater because it can impair some treatment equipment and can make process water for some industrial applications problematic or even unusable.

up over time, the silica and other scaling can require the turbine to be cleaned or even replaced. Semiconductor fabs use ultrapure water for cleaning and rinsing off etchant chemicals used during the manufacture of microchips. It is critical that this water is free from ionic and particulate contaminants (including silica) that could settle or precipitate on an electronic line of a chip and cause product defects. Typically, a semiconductor plant aims to produce an ultrapure water with a resistivity of at least 18.2 megohm-cm.

Concerns in Treatment Systems In water treatment, silica can also impact the systems and components. The best example is how it can scale RO and nanofiltration (NF) membranes to the point that they cannot be cleaned but must be prematurely replaced. This can become an expensive proposition. For example, RO elements can cost $500 or more. So, if a system has 150 membranes, the replacement cost could easily reach at least $75,000. For a smaller system of 10 to 16 elements, the replacement cost could range from $5,000 to $8,000. Figure 1 shows the end of an example of an RO membrane that is fouled with silica silicate scale. Figure 1: RO membrane fouled with silica silicate. Photo courtesy of David H. Paul, Inc. (Farmington, New Mexico).

End-User Concerns About Silica

Silica is a concern for different end users, but the power industry (and users of boilers for other purposes) and the microelectronics industry are two examples where silica in water can impact operations. At power stations, silica scaling can block boiler tubes or heat exchanger tubes in cooling systems. These blockages can endanger workers and cause plant shutdowns because of the risk of bursting boiler tubes or, in extreme cases, a boiler explosion. Silica can also carry over in the steam that drives a generating turbine and deposit on the turbine blades as a glass-like material. If allowed to build

Water Treatment Challenges

In water, silica is an umbrella term used to refer to three different forms: soluble (dissolved), colloidal, and particulate or granular. Silica is found in the different brackish water

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T.U.T.O.R. continued

sources used by treatment plants—groundwater, surface sources, and seawater. Reactive and colloidal silica content in groundwater and surface water can range anywhere from 1 up to 100 parts per million, or 1 to 100 milligrams per liter. Two common test methods used to detect silica are the Silicomolybdate Method for high-range measurement and the Heteropoly Blue Method for low-range measurement.

Unreactive or colloidal silica is a form of silica that is hard to detect in water and is slow to react to the molybdenum blue test. Colloidal silica has longer molecule chains of three or more and is often combined with other substances, such as iron, aluminum, or organics. This type of silica is predominantly found in surface water supplies.

Reactive (soluble) silica is found in surface sources and also is often a major contaminant found in groundwater. This form is called “reactive” or soluble silica. It forms yellow silicomolybdic acid via the reaction of ammonium molybdate and silica at a low pH in the molybdenum blue test method. This type of silica has short molecular chains of three or fewer silicas.

Particulate or granular silica is tiny particles of silica compounds such as clays, silts, and sand that are normally 1 micron (µm) or larger. This form is measured by the silt density index (SDI). Table A provides a summary about the different silica forms.

Table A: Silica Overview RO System Concerns

Type

Characteristics

Size

Where Found?

Removal

Particulate or granular

Silica particles from sand, silt, and clay.

1 µm or larger

Surface water

Lime softening, filtration

Silica particles can clog RO membrane pores.

Reactive or soluble

Dissolved form of silica that tends to have an anionic charge.

Molecular

Groundwater, surface water

RO, IX

Can precipitate and form scales.

Colloidal or unreactive

Suspended polymerized chains of molecules that contain tiny particles of silica. Commonly combined with other organic or inorganic compounds. Difficult to detect and remove from water.

10–100 nm

Surface water

RO, UF

Scaling.

Source: Table compiled by MD Henley & Associates.

Silica Removal From Water

Employing pretreatment systems is the most important step water treaters take to protect RO, NF, and other primary treatment equipment. These systems are designed based on the source water quality. Pretreatment steps can include coagulation/flocculation to remove suspended solids from the water as well as filtration steps (e.g., multimedia and cartridge filters) for particulate removal. In cases of hard water, a water softener can be used to remove calcium and magnesium. Treatment solutions. While silica can endanger effective operations and shorten RO membrane life, water plant operators can take steps to minimize problems. As mentioned, a good pretreatment system can provide feedwater to the primary treatment system to help prevent serious problems. Table B lists common methods used to reduce silica in water systems. Table B: Methods Used to Reduce Silica Soluble

Nonreactive

Granular

Lime softeners with elevated pH with the use of magnesium hydroxide

Lime softeners

Microfiltration

Hot process softeners

Hot process softeners

Clarification

Desilicizers

Macroreticular anion resin

RO

Upflow filters with chemical feed

Ion exchange

Crossflow microfilters

pH and water temperature adjustment

Ultrafiltration Membrane treatment chemicals to control fouling and scaling

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T.U.T.O.R. continued

For soluble silica, RO and ion exchange are listed by experts as ways to remove it from water. RO removes contaminants from the molecular range (greater than 0.001 µm) to the ionic range. Ultrafiltration, which removes contaminants in the molecular (less than 0.01 µm) and macro molecular (between 0.01 and 0.1 µm) ranges, is considered an effective way to take out colloidal silica. For granular silica, microfilters and particle filters are two approaches for removing this form that is sized 1 µm and larger. Clarification is also used.

In the Digging Deeper section, we have listed some resources, including water treatment books, that provide more background on silica.

In addition to the methods outlined in Table B, several types of RO treatment chemicals act as element cleaners and are used to protect RO membranes from fouling, scaling, and biofouling. These are added to the water. The goal of antifoulant and antiscalants is to keep contaminants suspended so that they pass through the RO system in the concentrate stream. Another step to protect and extend membrane life is Clean in Place (CIP), where the membrane system is taken offline. A CIP system is then used to clean the RO elements.

Comb, L. ( January/February 1996). “Silica Chemistry and Reverse Osmosis”, Ultrapure Water, pp. 41-43.

In this T.U.T.O.R. article, we have examined these topics: What is silica?

Digging Deeper Amjad, Z., ed. (1995). Mineral Scale Formation and Inhibition, ISBN: 0-306-45195-6, Plenum Press, New York, New York.

Amjad, Z., ed. (1999). Advances in Crystal Growth Inhibition, ISBN: 0-306-46499-3, Kluwer Academic/Plenum Publishers, New York, New York.

Amjad, Z., ed. (2010). The Science and Technology of Industrial Water Treatment, ISBN: 978-1-4200-7144-3, CRC Press, Boca Raton, Florida. Byrne, W. (2002). Reverse Osmosis: A Practical Guide for Industrial Users, 2nd ed., ISBN: 0-927188-03-1, Tall Oaks Publishing Inc., Littleton, Colorado.

Cotruvo, J. ( July 2015). “Contaminant of the Month: Silica and Silicates”, Water Tech Online, accessed at www.watertechonline.com.

Flynn, D.J., ed. (2009). The Nalco Water Handbook, 3rd ed., ISBN: 978-0-07154883-0, McGraw Hill, New York, New York.

Frayne, C. (2002). Boiler Water Treatment, Principles and Practice, vol. 1, ISBN: 0-8206-0371-6, Chemical Publishers, Gloucester, Massachusetts. Hach Co. (n.d.). “Silicomolybdate/Heteropoly Blue Method,” Hach Co., Loveland, Colorado, accessible through www.hach.com. Harfst, W. (April 1992). “Back to Basics: Treatment Methods Differ for Removing Reactive and Unreactive Silica”, Ultrapure Water, pp. 59-61.

Henley, M. (December 1992). “Colloidal and Soluble Silica Removal Remains a Challenge when Producing High-Purity Water”, Ultrapure Water, pp. 13-16. Henley, M. (March 1995). “Chemical Treatments Play Important Role for Efficient RO Operation”, Ultrapure Water, pp. 15-18.

Kucera, J. (2010). Reverse Osmosis: Industrial Applications and Processes, ISBN: 978-0-470-618431,John Wiley & Sons Inc., Hoboken, New Jersey. Manivasakam, N. (2011). Industrial Water Analysis Handbook, Part 2, chapter 60, ISBN-13/EAN: 9780820600406, Chemical Publishing, Gloucester, Massachusetts.

How does silica negatively impact traditional RO water treatment systems and end users of process water.

Meyers, P. (Oct. 18-20, 1999). “Behavior of Silica in Ion Exchange and Other Systems,” Paper No. 99-64, International Water Conference, Pittsburgh, Pennsylvania.

In a future article, we will look at other contaminants that also pose concerns for the professional water treater.

Closing Thoughts

Silica occurs in three forms in water—soluble, colloidal, and granular. Soluble and colloidal forms can cause scaling in RO systems and impact end-user products or operations equipment. Granular silica in water can leave water marks and cause scratches of smooth surfaces. In RO equipment, silica can damage membranes so that they must be cleaned or replaced more often. A water treatment plant can use membrane treatment chemicals as well as pretreatment technologies to remove silica from the water before the source water moves to the primary treatment plant.

Paul, D. (May/June 1998). “Back to Basics: Understanding a Water Analysis—Silica”, Ultrapure Water, pp. 64-65.

Smith, C.H. ( July/August 1993). “Usage of a Polymeric Dispersant for Control of Silica”, Industrial Water Treatment, pp. 20-24.

Tan, P. (2008). Optimizing a High-Purity Water System, ISBN0-9218811-2, Tall Oaks Publishing Inc., Littleton, Colorado. US Water Systems (n.d.). “What Is the Best Way to Remove Silica from Water?”, U.S. Water Systems blog, accessed at www.uswatersystems.com.

Do you have an idea for a T.U.T.O.R. article? We are interested in topics that touch on different aspects of water treatment and would welcome your input. If you have an article idea, please contact Mike Henley at mdhenleywater@gmail.com or (303) 324-9507. Mike Henley is a water industry consultant through MD Henley & Associates. He also serves as technical editor of The Analyst.

75 the ANALYST Volume 28 Number 4

Business Notes

3 Strategies for Managing Profit-Draining Customers Jonathan Byrnes and John Wass, Profit Isle

Managers today have a huge, unaddressed opportunity to engage and manage their large, profit-draining customers, creating win-win relationships that rapidly increase profits and lock in these key customer relationships. As yesterday’s mass markets fragment, managers must shift from broad-based product management to highly focused management of target customer segments—and even individual customers. In previous articles, we described transaction-level profit metrics, an innovative new set of digital transformation metrics. When companies use these metrics (creating an all-in profit and loss statement for every invoice line), they quickly see that their customers fall into three broad profit segments: —PROFIT PEAKS: High-revenue, high-profit customers (typically about 20% of the customers that generate 150% of their profits); —PROFIT DRAINS: High-revenue, low-profit/loss customers (typically about 30% of the customers that erode about 50% of these profits); —PROFIT DESERTS: Low-revenue, low-profit customers that produce minimal profit. The potential profit increase from turning around money-losing customers is huge. Here’s how managers can turn their profit-draining customers into profit peaks: 1. REDUCE COSTS ON BOTH SIDES: In our experience, customers are rarely profit drains because of below-market pricing; they’re profit drains because serving them entails an excessively high cost, generally caused by relatively minor factors that are unseen and unmanaged. The good news is that this is often relatively easy to fix: You can create a win-win solution for both

companies, increasing the customers’ own profitability while converting many into profit peaks. We call this process of joint cost reduction (increasing profitability by lowering the cost to serve rather than raising prices) conditional pricing. For example, a distributor we’ll call Harbor Supplies (not its real name) recently decided to install vending machines loaded with its products in its large customers' spaces. Harbor’s financials showed that this business produced strong revenue growth and gross margins. When the company implemented its new digital transaction-level profit metrics, however, the managers saw that the vending business was actually draining net profits. The vending segment’s detailed profit and loss statement clearly showed that the problem was that the customers were ordering replenishments several times a week. The cost of picking and shipping an order was higher than the gross margin—a common problem that went undetected by the traditional financials. This was just as costly for the customer as it was for Harbor. Fortunately, this was easy to remedy: The sales team inserted a replenishment frequency clause into the contracts and met with the customers to explain how this would lower the customers’ ordering and put-away cost, creating a win-win. Virtually all of these profit-drain customers became profit peaks. 2. ASSIGN THE RIGHT TEAMS TO THE RIGHT CUSTOMERS: Once you’ve identified your profit-draining customers, the next step is to engage and manage them with specialized teams focused solely on building ongoing relationships in order to lower the cost to serve them—and often lowering the customers’ costs in the process. Since the profit-draining problems are most often lower-level operating issues, such as order patterns, the team should consist of specially trained operating managers.

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Business Notes continued

New digital transaction-level metrics are critical for identifying opportunities for win-win cost savings because virtually all of the operating cost improvements are not related to price. Most companies engage their large customers with the implicit objective of raising prices, creating a zero-sum relationship. Teams created to address profit-draining situations, on the other hand, have the explicit objective of lowering costs for both vendor and customer, creating a win-win relationship. For example, Natco Distributors (not its real name), a national industrial distribution company, had always provided next-day service to its customers. Many times, this involved costly expediting and shipping from a central warehouse if a local distribution center had run short of stock on a product. This was very costly and caused several major customers to be profit drains.

—Order channel: Most companies are rapidly moving toward electronic data interchange, or EDI, because it offers significant cost saving. However, with EDI orders—essentially, electronic orders—you miss out on the opportunity to cross sell, upsell, and probe for important customer information. We suggest companies use EDI for small customers to lower the cost to serve, while selectively calling back the most important clients once the EDI order is received to cross-sell, upsell, and keep the relationship close. In continuously working with profit draining customers, your teams will gain a deep understanding of the profile and development pathways of these customers—as well as the operating cost problems that can be fixed. This will enable you to identify which prospective customers are likely to become intractable profit drains.

When Natco assigned a specialized team to spend time with these customers, its members saw that in many cases the company didn’t need overnight service. The team partnered with counterpart managers from the customers to identify the shipments that really required overnight service. This change reduced the expediting and cross-shipping costs for Natco, turning these customers into profit peaks. In return, Natco guaranteed 100% order fulfillment on the scheduled dates (which eliminated inefficient back orders).

This knowledge is invaluable. Your teams need to partner with your sales managers to incorporate these profiles into your account selection and management processes. This will allow them to laser-focus on bringing in the accounts that will be profit peaks or that could be converted into profit peaks and avoid those that will be irreversible drains. Over time, your sales representatives will learn to avoid customers who will irreversibly erode your hard-earned profit. And that is the biggest hidden profit lever of all.

3. CONSIDER THREE COST ITEMS: In our experience, a small number of cost items offer many of the best opportunities for improvement:

Jonathan Byrnes is founder and chairman of Profit Isle, where John Wass is CEO. © 2020 Harvard Business School Publishing Corp.

—Order pattern: Like in the vending machine example, this factor is rarely managed. It’s relatively easy to change in most cases, and it offers important gains for both the supplier and the customer. —Product mix: In companies without digital transaction-level metrics, the sales and product managers don’t know each product’s actual net profit. Transaction-level metrics reveal each product’s net margins, enabling product managers and sales reps to optimize product mixes for profitability at no cost to the customer.

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Advertising Index 33 American Water Chemicals, Inc.

13 North Metal & Chemical Company

51 AMSA, Inc.

15 Pulsafeeder, Inc.

43 Brenntag North America

57 QualiChem, Inc.

78 Browne Laboratories, Inc.

61 Radical Polymers

21 Chem-Met Company

64 Sanipur US LLC

53 CHEMetrics, Inc.

80 Special Pathogens Laboratory

19 EMSL Analytical, Inc.

50 Uniphos, Inc.

2

79 Walchem, IWAKI America Inc.

Environmental Safety Technologies, Inc.

5 IDEXX

7

WaterColor Management

40 Myron L. Company

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