Article Boiler Dissolved Oxygen BOILER WATER DISSOLVED OXYGEN CONTROL DO Chemistry Dissolved oxygen is a measure of the amount of ‘oxygen, usually thought of as a gas, that is dissolved in a liquid such as water. Oxygen is essential to life and is the most common element found taking part in corrosion reactions. It is this corrosion reaction that provides the main need for trace (boiler) dissolved ‘oxygen analyzers, such as IC CONTROLS 885 which is designed to run, normally, at part per billion (pb) levels. Dissolved Oxygen can be thought of as the food needed for the corrosion process to proceed. Oxygen is highly corrosive when dissolved in water. Mechanically hard and porous metal oxide deposits have little strength and form rapidly in the presence of water and oxygen, plus the most serious aspect of ‘oxygen corrosion is that it occurs as corrosion cells that can result in pitting. Pitting is a concentration of corrosion in a small area of the total metal surface that effectively drills a small metal oxide filed hole in the metal. Pits by driling through the metal can produce failures even though only a relatively small amount of metal has been lost and the overall corrosion rate islow. Rapid corrosion will progress inside an industrial or utility boiler water and steam system unless dissolved ‘oxygen can be virtually eliminated. Unchecked corrosion eventually results ia expensive repairs or equipment failures and subsequent replacement. Boiler water DO removal Dissolved Oxygen removal from any steam and water system is of major importance. The first step is typically mechanical deaeration which is economical oxygen removal and serves to eliminate other corrosive gases such as ammonia and carbon dioxide. A properly operated deaerator can reduce dissolved oxygen to as low as 20 ygil. (20ppb). Note: tyg/L =1ppb. For complete oxygen removal down to low ppb levels a second step, chemical oxygen removal, is needed to assist the deaerator.Itis important to monitor the actual dissolved oxygen level since air contains 20.99% ‘oxygen and the difference between the atmosphere percent and ppb is a factor of 100,000,000. Thus, any tiny leak in the equipment will result in high dissolved ‘oxygen and corrosion. More economical dissolved ‘oxygen removal can be achieved by measuring 40H Lead anode Po-> Pt + 26 Electroiyte solution Figure 1 Basic Galvanic Cell (G ConTROLSArticle Calibration At any given temperature and barometric pressure the Partial pressure of oxygen in water-saturated air is exactly the same as itis in alr-saturated water. Thus a ‘sensor can be calibrated in water-saturated air, using the 20.9 % oxygen available in air as the full-scale standard, and it will correctly read dissolved oxygen in water samples. Both temperature and barometric pressure affect the partial pressure of oxygen in air saturated with water vapor. The 865 has automatic temperature and barometric pressure sensors, so itcan automatically obtain the correct data, look up the dissolved oxygen table, compute the correct gain, and calibrate the analyzer. To calibrate the sensor, simply suspend the probe above water and let the analyzer auto calibrate. This calibration technique will give a 100 % saturation reading for the temperature and pressure which the 865 will display as ppm dissolved oxygen, Figure 2. ppb D0 Calibration Figure 4 Closed Hot-Water Heating System Boiler Dissolved Oxygen DISSOLVED OXYGEN CONTROL OBJECTIVES ‘Successful water treatment in closed (or almost closed) systems such as boiler and steam, hot-water heating or chilled water systems has three fundamental requirements that must be met. 1. Dissolved oxygen concentrations must be controlled to reduce the likelihood of forming ‘oxygen corrosion cells that can result in pitting of carbon steel 2. The pH must be maintained high enough to ‘minimize general corrosion of carbon steel, but not so high that caustic attack can occur. 3. An external-treatment system must be in place to minimize the ingress of dissolved and suspended solids andor an internal treatment ‘system must be used to control these materials. Looking at the first item, dissolved oxygen control Target values specified by most manufacturers and utilities have called for oxygen concentrations in boiler feedwater or closed heating/cooling systems to be kept below 5-10 ug/L. Achieving this low level of oxygen ‘may require a combination of mechanical and chemical methods in systems such as the boller in Fig. 3, Ra —} £ =) ke) me { _ Figure 3 Boller Steam and Water Cycle Other systems, such as a closed hot water heating or cooling system, particularly when they are tight (no oxygen inleakage points), may achieve their target with only the chemical addition. The hot-water heating system in Fig. 4 uses only a by-pass feeder for intermittent chemical feed, 29 Centennial Road, Orangeville, ON, L9W IRI 1-800-265-9161 www.iccontrols.com (519) 941-8161 Fax: (519) 941-8164 E-mail: sales@iccontrols.com (€ contRoLsArticle MECHANICAL DEAERATION ‘As new make-up water is fed to the boiler, or condensateis recycled back, it goes through the deaerator or deaerating heater. The principle behind the deaeration process is Henry's Law of Partial Pressures. The solubility of a gas in a liquid is proportional to the partial pressure of the species in the atmosphere in equilibrium with the liquid. In this case, the make-up water has been in equilibrium with the atmosphere and the solubility of oxygen and nitrogen has been proportional to the concentration of oxygen and nitrogen in the atmosphere. In the raw water, this Corresponds to 8-10 ppm of oxygen. In the deaerator, the water equilibrates with steam. As oxygen and nitrogen are now excluded, the dissolved gases must leave the liquid to enable the equilibrium tobe achieved. Deaeration is performed in two stages. a. Inthe first stage, the feedwater is sprayed into the deaerator vessel where it contacts a flow of ‘steam, The steam both heats the water to within ‘a degree or two of the steam temperature and removes most of the dissolved non-condensable gases. b. Inthe second stage intimate and vigorous mixing Of the liquid and steam removes the remaining non-condensable gases. The steam and gases that were removed from the water are vented to the atmosphere. In a property operating system, a plume 1-1.5 meter high would be seen above the vent. If the plume is lower or higher, the steam flow should be adjusted. ‘The heated water then moves to the storage tank until needed by the boiler. Typically, oxygen can be reduced to 20 ugiL or lower. The major manufacturers such as Ecodyne make both scrubber and tray deaerators. The expected performance from both types of deaerators can be 10 ug/L or better under steady load conditions. {As the contact between the steam and liquid water will change with flow, it can be expected that the actual Performance will be somewhat dependent upon the plant load, Of the two types, the scrubber unit can tolerate operation over a wider load range (typically 20-120% of design) than the tray unit (typically 40-100% of design) which can tolerate more cold water. The tray unit is generally the choice in the bigger units that operate under constant load as in major electrical generating stations. When conditions depart from the design conditions, there may be some deterioration in the concentration of dissolved oxygen that will be achieved by the Boiler Dissolved Oxygen we fA cxomtene Figure 5 Simplified deaerating Heater deaerator and within thé system. To compensate for ‘any changes, the water is chemicaly treated to remove any residual oxygen as itis fed to the storage tank Chemical treatment becomes economical only after the bulk of the oxygen has been removed “mechanically” with the deaerator. if used eatler, the costs would be | prohibitive. Trying to ensure an oxygen-free environment by adding and monitoring a large excess of oxygen scavenger has been shown ineffective by continuous on-ine ppb DO measurements revealing the coexistence of dissolved oxygen and resulting corrosion. It is important to ensure that only a smal excess of scavenger is added and that the dissolved oxygen is monitored on a regular basis to see the performance of the deaerator The deaerator is designed to operate for extended periods with no attention other than adjustments to the steam flow. With continuous on-line ppb DO measurement the operators can optimize steam flow for the lowest ppb reading, plus automation becomes possible. Annual maintenance is a visible inspection to ccheck that the sprays respond to pressure properly and that all internals are present and supported as designed. Should the support for the baffle system be disturbed a short circuit in the flow pattern could develop. If this resulted in a reduction of oxygen removal capacity within a particular region, localized pitting or grooving may be visible. With continuous on-line ppb DO measurement and any of these problems, you see performance deteriorate and action can be taken before serious damage is done, plus IG ConTROLSArticle chemical scavenger costs will remain under control On systems with a turbine, non-condensable gases (air) are also removed by vacuum pumps or ejectors operating with the condenser to help achieve the desired vacuum or backpressure for efficient operation Of the turbine. In a typical condenser system (Fig. 6), the dissolved oxygen can be reduced to 20-50 g/L by the ojectors and the deaerator completes the job to bring the dissolved oxygen down to the 10 jigiL range. In some plants with a very tight condenser and feedwater system, it is possible to get this low concentration with the condenser ejectors alone. A number of steam generating systems actually do ‘ lw 7 power Figure 8 Typical Condenser System for Turbine ‘operate with the condenser alone and no deaerator. CHEMICAL DEAERATION There are a number of chemical species that rapidly react with oxygen. Several of these are suitable to act fas oxygen scavengers. These fit into two categories, which are the sulfites and the weak bases, including hydrazine and its substitutes. Sodium sulfite: This product is used extensively on low-pressure boilers, below 1000 PSI. Although reasonably priced and easy to handle, it contributes, ionic solids to the system thereby adding to corrosion and scaling potentials and requiring more blowdown. Plus, it is able to passivate metal surfaces only at elevated temperatures. 2NazSO3 + 02> 2NazSOs The reaction product is an ionic salt. Depending upon the supplier, it may also be purchased as a bisulfite such as NaHSO3, Whichever product is used, it Boiler Dissolved Oxygen contributes to increased conductivity in the water. Under appropriate scale forming conditions, a sulfate-containing deposit could be formed. The dosage, ona mass ratio basis, requires 8 mg/L foreach mg/L. of oxygen. Sodium sulfite alone is slow to scavenge oxygen from boiler feedwater. The rate of reaction is considerably hastened by the addition of a small quantity of a heavy metal cation salt such as iron, copper, cobalt, and nickel salts as a catalyst. Caution; the catalytic action can be deactivated by several products commonly used for boiler treatment. ‘Addition of catalyzed sulfite plus any phosphate product from the same addition tank will, as an example, result in deactivation of the catalyst. Sodium sulfite is available as an open-market commodity. The catalyzed sodium sulfite is a blended product and can be purchased at higher cost from industrial water treatment companies. Selecting sodium sulfite or hydrazine involves, consideration of the byproduct salts, cost of blowdown, handling safety, DO removal effectiveness, and available technical support. Because hydrazine’s oxygen scavaging byproducts are water and nitrogen it has no adverse effect on corrosion or blowdown. Hydrazine also as a reducing agent cuts corrosion by passivating metal, it would seem a the Ideal choice. ‘There is, however, a preference in some locations to use sodium sulfite over hydrazine because of reported greater safety and lower costs. Neither of these is totally vali. i) The required dosage for hydrazine is much lower than that of sodium sulfite, and its contribution to blowdown is negligible. It's also a less expensive product when corrected for scavenging capacity. ‘There are no reported deaths due to hydrazine exposure in spite of the perceived risk associated with its use. ii) lil) There are several deaths each year attributed to sodium sulfite. Although sodium sulfite is a ‘common additive to foods as a preservative (it keeps meat looking red and lettuce green), concentrated sulfte can trigger severe allergic reactions which can result in death to people with asthmatic and other conditions that make them particularly sensitive. Hydrazine: Hydrazine can act both as an oxygen scavenger and as a reducing agent to passivate metal surfaces. It combines with oxygen and the end products are nitrogen and water: 29 Centennial Road, Orangeville, ON, LOW IRI 1-800-265-9161 (519) 941-8161 Fax: www.iccontrols.com E-mail: sales@ jecontrols.com (519) 941-8164 (1G conTROLSArticle (Op + NoHa > 2H20 + No ‘These hydrazine oxygen reaction end products, water and nitrogen gas, clearly have of no adverse effect on the system. At higher temperatures the hydrazine decomposes to yield ammonia: SNoH4—>4NHa+N2 T= 200-920 °C 2NoHa > 2NHg + Ho + Ne T » 320°C Carbon steel (iron) and copper surfaces are passivated by the formation of a protective oxide layer. In the case of the carbon steel, the protective surface is the black magnetic oxide (magnetite, FesO.). and for copper Cuz0 that both resist further attack and remain stable for years: @Fe203 + NoHa > 4FesOs + 2He0 + No 6CUO +NeHy > 4Cu20 + 2H20 + No It should be noted that zero oxygen is not actually a desirable target. A small trace of dissolved oxygen is actually desirable to allow some very limited corrosion to occur so the hydrazine can then go about doing its job of converting rust to magnetite. This repair ‘mechanism provides a more impervious passivating layer on the carbon steel surfaces. Often a catalyst is added to accelerate the oxygen scavenging rate, The most commen catalyst is hydroquinone, which itself is used as an alternative ‘scavenger. At lower temperatures, as in a closed cooling system, the use of the catalyst may be valuable. ‘At higher temperatures, there is likely enough metal oxide surface within the system to make it self-catalyzing. Hydrazine adds insignificant solid or ionic material o the system. While itis ideal for the job, it has come under attack due to various claims about potential carcinogenic nature. As a result, various alternative products have been brought to the market. “Hydrazine Substitutes”: Carbohydrazide: In a way, this appears, at first, o be another way of adding hydrazine as the product is @ condensation product made from hydrazine and @ carbonyl group (e.g., carbon dioxide). It dissolves in water to release hydrazine: ° I HN,-C-NH, = HO = 2NH, + CO, Carbohydrazide is also capable of scavenging ‘oxygen, on its own, without reverting back to hydrazine: ° i 20; + HyNy-E-NHy = 2N, + 3H,0 + 00, Boiler Dissolved Oxygen Caution Carbohydrazide releases of carbon dioxide into the system which must be treated to prevent corrosion. Sufficient neutralizing capacity must be present to prevent any corrosion from its presence. Diethylhydroxylamine (DEHA): The primary reaction ‘consumes oxygen to yield acetic acid: on ° r + AH,C,-N-CH, - BH,C-C-OH + Ny + 61 on In realty, the reaction does not always proceed by a simple straight forward route and a number of side products, including acetaldoxime and acetaldehyde may form. In the end, these may result in the formation of weak organic acids. Hydroquinone: This material is the most common catalyst used with hydrazine, It can also be used cefectively by itself. The scavenging reaction produces water and benzoquinone: 2H0-G}-0H + 0, = 2H,0 + 204250 ‘The benzoquinone formed may further decompose to form some light alcohols and ketones. There is also some possibilty of linking the benzoquinones into a chain structure. Methylethylketoxime (MEKO): When oximes react with water, the C=N bond is broken and a ketone is, formed: N-OH ° 0, + HyC-C-CH, = HyC-C-GH, + N,0 + HO This product may decompose in high-pressure boilers to release ammonia: N-OW ° 1 1 H,C-C-GiH, = H,C-C-CMy = NO + HO +N, + NH, ‘The ammonia presents no problems. The ketone may ultimately end up as some combination of weak organic acids and possibly some polymer. Erythorbie Acid: This product is a stereo isomer of ascorbic acid or vitamin C (it is essentially the same molecule, buta mirror image). The body's functions are stereo specific. They will not accept this molecule as it just doesn't fit. The main reaction is: +40. 0 + Ho no o Eicon Yuchion on on (€ CoNTROLSFurther degradation under boiler conditions will eventually lead to the formation of a series of weak organic acids including lactic, glycolic and ultimately carbon dioxide. Vitamin C would undergo the identical reactions. Hydrazine vs Substitutes: Is there any distinct advantage provided by the hydrazine substitutes when ‘compared to hydrazine itself? They are all capable of doing an excellent job of scavenging oxygen and they all passivate iron and copper surfaces. The differences may be more commercial than technical. With substitutes you get application assistance, technical support, a product that is easier to handle, but costs, more. Hydrazine has not been proven to be a carcinogen. There is even some reported use of hydrazine ‘compounds for the treatment of cancer symptoms. Some of the most safety conscious organizations continue to use hydrazine and have no plans to change. ‘These include the electrical utilities and NASA, where hydrazine is used as a propellant. In the mg/L region, itis an oxygen scavenger. At full strength it's reaction with oxygen produces a powerful rocket fuel. Hydrazine is an obnoxious material to handle, but simple closed handling systems are available that eliminate most of the handling hazards. A recent test showed insignificant levels in the building following a deliberate spill ‘Most substitutes cost only about 10-20% more than hydrazine on a $per-kg basis, but they may require dosages as much as 5-10 times higher because they are actually much heavier molecules. The comparison must be made on a mass ratio basis. By coincidence, the mass of one mole of oxygen and hydrazine are equal, meaning that 1.0 mg/kg of hydrazine reacts with 1.0 mgIL of oxygen. Comparison of Oxygen Scavangers Material mole Mass Ratio oxygen 7 820g 1.00 hydrazine 82.09 1.00 lcarbohydrazide 42.09 1.31 DEHA (diethylhydroxylamine 70.09 4 19 ymethylethyiketoneoxime «7.09 2.72 Erythorbie acid 176g 5.50 ‘Sodium sulfite (monohydrate) 142g 4.49 29 Centennial Road, Orangeville, ON, L9W 1R1 1-800-265-9161 www.iccontrols.com (519) 941-8161 Fax: (519) 941-8164 E-mail: sales@iccontrols.com Boiler Dissolved Oxygen On a ratio basis you can see less hydrazine, by weight, is required to scavenge dissolved oxygen in the system, Another factor to consider is that organic residues may lead to boiler tube failures and are the subject of a number of research projects now in progress. This may be a substitution of one control problem which is easy to control for another. One interesting research project (Gilbert and Lamar, Hydro-Québec) has shown thal the breakdown reactions of some organic species consume oxygen. ‘One of the species studied was morpholine which was added for pH control rather than as an oxygen scavenger. Degradation products included carbon dioxide, acetic and glycolic acids. With the ability now to measure them, these weak acids have become a concern with respect to corrosion of the metal surfaces. ‘Two nuclear generating stations, Gentilly-2 in Québec, Canada and Tihange in Belgium, now operate without the use of an oxygen scavenger; they rely upon the indirect scavenging of morpholine, coupled with a tight system. Similar reactions exist for most organic species under boiler conditions. Inevitably they end up ‘as some combination of carbon dioxide and other weak acids. OC) exo) e 7 | r | i + cen om te Jo. freer ‘When selecting an oxygen scavenger for your plant, safety, cost and your technical support needs, should be considered the determining factors. All the scavengers discussed have their advantages and should be considered depending on your plants technical abilities and oxygen scavenging needs. IG conTROLSArticle OXIDIZING CHEMISTRY ‘Therehas been a recent move, particularly in Germany, Russia and some US utilities, toward oxidizing chemistry. Instead of adding an oxygen scavenger to remove oxygen, a low level of oxygen is maintained Typically oxygen is controlled in the 50-200 pg/L range. This chemistry has some advantages. It forms an ‘pron oxide tlm that can be both stable and protective. ‘The solubility of this oxide species is somewhat lower than that of the magnetite, formed with hydrazine, and could result in much lower transport of iron. on, pb Figure 7 Feedwater in a Supercritical Unit Note; The low iron at high dissolved oxygen levels needs very low cation conductivities. (trom EPRI data) This mode of operation is neither a contradiction nor a substitute for low oxygen programs. As the research data following shows, it represents a reasonable operating regime under a set of limiting conditions. To be able to use it, extremely tight control of the system chemistry must be maintained at all times; there is no margin for error. The water purity must be maintained sufficiently high, ie., a cation conductivity .15 yS/em (015 mS/m). With this purity, the corrosion rate for carbon steel drops dramatically and a more stable and protective oxide is formed in the presence of oxygen at concentrations in the range of 50-200 ygiL. It is important to recognize that if the purity can not be maintained, the corrosion rate will increase. Depending upon the tightness of the system, the deaerator may only be needed during startup. Alternatively, a smaller deaerator may be used with the intent of deaerating only the makeup water. It is conceivable that some systems may add oxygen from bottles rather than depend upon air ingress. As discussed earlier, it should be noted that there is a requirement for oxygen to complete the breakdown of the various products to carbon dioxide and weak ‘organic acids. With oxygenating conditions, sufficiently large quantities of oxygen are available to assist in the Boiler Dissolved Oxygen breakdown of any organic material present within the oiler system. The use of volatile amines should be restricted to ammonia to prevent excess formation of ‘weak organic acids. There is operating experience to show that under oxygenating conditions, there is no longerthe same need for operating at a historically high ten corona m- 207 Fig. 8 pH Dependance of corrosion-product release H to protect the carbon steel surfaces. EPRI data, Figure 8, indicates that operation under neutral conditions provides essentially the same level of protection providing the above purily restrictions can be met. Many small combined cycle plants operate under these conditions as it simplifies the water chemistry. CYCLING from Reducing to Oxidizing There is a vast difference between the reducing » conditions with chemical treatment for low oxygen conditions and the oxidizing conditions for oxygenated treatment. Switching from the one set of conditions to the other places a severe stress upon the system. Le Chetalier’s Principle states that a system under stress will move in a way to relieve that stress. In most cases, this results in a tendency to strip off the existing oxide surface layer and replace it with a new surface layer formed under the new conditions. ‘The high level of particulate material could result in plugging of small bore flow paths such as flow orifices or the path within the capillary or drag valves used for pressure reducing and water sampling. ta system cycles between the two states, itis likely that the repeated loss of surface will result in excessive wall thinning and eventual failure. With proper controls, this cycling can be utlized to bring about a cleaning or decontamination of system surfaces. At the Douglas Point nuclear station, in Canada, this technique was used fo decontaminate the primary circuit. This circuit operates normally under reducing conditions. Prior to ‘a weekend shutdown, oxygen was added to make the Conditions oxidizing. When the shutdown occurred, the rapid change of heat flux, coupled with the change to oxidizing conditions, resulted in a sudden release of large quantities of magnetite from the boiler and piping 6 CONTROLSArticle surfaces (which contained a significant proportion of the °Co {cobalt 60] that caused the radiation fields). This was then removed by the purification system Repeating this process several times over a few months succeeded in removing a considerable portion of the radiation fields from the boiler and piping surfaces and ‘enables maintenance to go ahead with less expended radiation dose. DISSOLVED OXYGEN CONTROL There are two components that must be monitored First, its important to monitor the quantity of residual dissolved oxygen present in the system. Then it is important to assess the effects of this oxygen. This lattoris best assessed by measuring the quantity of ron Circulating within the system. ssolved Oxygen In boiler plants and closedoop heating or cooling systems, there is a need for ug/L. (ppb) analysis. The methods and equipment used for these measurements are considerably afferent than those for doing the mg/L (Part per mition) range that would be common in a raw water supply. Collection ofa grab sample presents the major difficulty. As soon as any sample is taken from the system, it is surrounded by air which contains 20.99% oxygen. The difference between oxygen in ait land ppb boiler water dissolved oxygen is a factor of 100,000,000. Any trace of oxygen in-leakage contamination will result in a high reading. Only Permanently installed, on-line ppb dissolved oxygen analyzers that become part of the system with a continuously flowing sample will properly resist inseakage errors. To overcome the grab sampling difficulties, a common approach has been to maintain a sufficiently high concentration of oxygen scavenger so that the presence of any dissolved oxygen is unlikely. For many such systems the concentration of the inhibitor was actually specified as the control parameter. This approach has suffered failures in the past where oxygen was present but had not been detected because dissolved oxygen was not being monitored, After the failures it's presence was usually inferred from the forensic work that was required to ascertain why boiler tubes or an economizer had failed, The logic for using the scavenger as the control parameter is based upon claims that any analyses for ‘oxygen will be meaningless. The explanation is that an ‘excess of scavenger will sooner or later eat up the residual oxygen. This logic ignores the competitive chemical reactions that could occur and may even be Boiler Dissolved Oxygen more likely. The reaction rates for oxygen scavenging are usually based upon laboratory work performed within glass apparatus. An industrial boiler is usually constructed from carbon steel or some more exotic alloys. It can be considered as being an iron oxide surface. The residual oxygen can react with this surface or it can react with the scavenger. Which will be favoured? The answer to that is dependent upon conditions within the system. The fact that boiler, ‘economizer or superheater tubes have failed from oxidative processes, on boilers using high residual scavenger, verify that maintaining a large residual of scavenger may not provide sufficient protection Maintaining control based on excess concentration of scavenger increases scavenger treatment costs. The higher ionic content will also require more blowdown, which also consumes more of all boiler treatment products and may also waste energy if there is no blowdown energy recovery system. From a control point of view, monitoring for high residual scavenger alone has some serious disadvantages. By comparison, dissolved oxygen measured directly on-line, even combined with residual scavenger measurement, produces a better overall view of boiler conditions and pays for itself through reduced blowdown and treatment chemical costs. Dissolved oxygen may be determined with relatively inexpensive test kits based upon color comparison. In the most common test kit, the color forming reagent is blue indigo dye which is very prone to rapid oxidation in the presence of oxygen. Its unoxidized form has a faint yellow color, which quickly changes to violet as it is oxidized. The level of oxygen is determined by ‘compating the color produced vs. a set of standard colors. A number of test kits are available. All must be handled carefully to avoid air contamination; however, with practice, fairy good readings can be obtained. Although itis common to get a number of high readings, with practice readings made down to the 5-10 ug/L range, with an operator with good blue recognition, good lighting, and who can take the reading soon enough that incoming atmospheric oxygen has not pushed the reading high. It must also be remembered when measuring dissolved oxygen that an oxygen ‘scavenger is present and it will eventually remove the ‘oxygen, so the sample cannot be transported or stored, To avoid losing oxygen, itis imperative that the analysis be performed quickly. This means that the test kit must bbe taken to the sample point rather than taking the sample back to the laboratory. Whenever critical measurements are required, asin the operation of a boiler plant, a permanently installed 29 Centennial Road, Orangeville, ON, LOW IRL 1-800-265-9161 www.iccontrols.com (519) 941-8161 Fax: (519) 941-8164 E-mail: sales@iccontrols.com (6 coNTROLSArticle conviine ppb aissolved oxygen analyzers the best route to obtain consistent readings that avoid contamination. in the detector, oxygen is measured by an clectrochemical cal which i isolated from the solution with a thin membrane through which the oxygen diffuses. A typical modern oxygen analyzers might cost | enn Figure 9 865 ON-LINE ANALYZER $6-10,000. As little as an hour per month of maintenance Is often sufficient to keep the analyzer operating. Recent advances with these on-line analyzers have seen the arrival of portable units that can be easily and quickly hooked up to a sample point and the sample logged, then quickly disconnected and moved to log another sample point in the system, ‘These portables can then transmit the sample data via your serial port to your computer. With a combination Cf on-line ppb dissolved oxygen measurement at the deaerator and a portable on-line ppb dissolved oxygen to monitor various potential oxygen in-leakage points, ‘a true picture of the condition of any boiler system can bbe obtained, plus cost efficient action can be directed where itis needed. Boiler Dissolved Oxygen Circulating Iron Concentrations The best indication of good dissolved oxygen control, Js the concentration of iron circulating around the system, Iron content can be determined by either 869 PORTABLE DO taking a sample for chemical analysis or by passing a large volume of sample through a particulate filter to catch the suspended solids. This latter approach is ‘accomplished using comparison charts which also give ‘some indication of the chemical state of the iron by its color. In a well controlled system, concentrations of Circulating iron can be expected to be consistently below 10 pg/L. Under reducing chemistry, the iron should be present as the black magnetic oxide, magnetite or FegO4. Under oxidizing conditions, the iron should be present as a brown iron oxide. 865-25 Online-Calibration DO Analyzer (G CONTROLS .Article Boiler Dissolved Oxygen Saturated Dissolved Oxygen Values The table below shows the concentration of dissolved oxygen in water over a range of temperature and pressure. Dissolved oxygen values are reported as parts per million. The analyzers use the table to calibrate the DO sensors. ren Ce 0) Ce Ce ya ae te 0 1351 1365 1380 1394 1409 1423 1497 1452 1457 1467 1481 1495 15.10 1525 1 1815 1329 1343 1357 1371 1985 1399 1419 14.17 1427 1441 1456 1470 1484 2 1279 1298 1306 1320 1334 1348 1361 1375 1379 1988 1402 1416 1490 1443, 3 1246 1259 1272 1286 1299 1313 1325 1939 1343 1952 1268 1379 1993 1406 4 1243 1225 1238 1252 1265 1277 1290 1304 1308 1317 1929 1242 1356 1369 S 1162 11.95 1207 12.20 1299 1245 1258 1271 1276 1283 1298 1309 1921 1934 6 1152 1164 1176 1189 1201 1213 1225 1298 1242 1250 1262 1275 1287 1300 7 M29 11.98 11.48 1160 1172 1184 1196 1208 1217 1220 1292 1244 1256 1268 8 1095 1107 11.19 1190 1142 1154 1166 1177 1187 1189 1201 1219 1225 1297 8 1069 1081 1093 1104 1118 1127 1199 1150 717.53 1161 1173 1185 11.96 1208, 10 1044 1055 1065 1077 1089 1100 14.11 1122 1726 1198 1145 1158 1167 1179 11 1020 1081 1042 1052 1064 1075 1086 1096 1099 i108 1119 1190 1140 1182 32 396 1007 10.17 1028 1039 1050 1060 10.71 1074 1082 1093 1109 1114 1124 13° 974 984 995 1005 1016 1026 1037 1047 1050 1058 1068 1079 1089 11.00 14 952 962 9.72 983 993 1003 1013 1024 1027 10.34 1044 1054 1065 1075 18 931 941 952 962 972 981 992 1002 10.05 10.12 1022 1092 1042 1052 16 911 921 931 941 851 960 970 980 989 990 1000 1010 1020 1028 17 892 902 912 921 931 941 950 960 969 970 979 9a9 999 1008 18 874 883 892 902 912 921 930 940 943 950 959 998 978 987 19 856 866 875 884 899 903 912 O21 924 931 940 949 958 967 2 829 48 857 865 875 BBs 893 903 905 912 921 990 029 947 21 823 892 B41 850 859 B67 876 885 888 B95 904 913 O21 9.90 2 807 815 824 833 842 B51 859 863 871 B77 A868 895 903 9.12 23° 7.92 800 809 818 826 835 B44 852 855 861 870 879 887 896 24 777 785 794 802 811 819 828 836 839 845 853 862 870 879 2% 763 771 7.80 7.88 796 804 813 821 824 850 838 847 855 864 2% 749 (757 765 773 782 7.90 798 806 809 815 823 831 839 848 2 736 744 752 780 768 776 784 792 7.95 801 809 817 825 B33 2% 723 731 738 748 755 763 770 778 781 787 795 802 810 B18 2% 710 718 726 794 742 750 757 765 768 773 781 7.89 797 805 90 698 706 7.19 7.21 729 787 744 752 755 760 768 776 7a 7.91 3B 687 694 702 709 717 725 792 740 742 748 755 763 771 778 82 675 683 690 698 705 713 720 728 730 795 743 750 758 765 83 664 671 679 886 694 TOI 709 716 778 723 731 738 746 759 34 653 660 667 675 682 690 697 705 707 712 719 726 734 Tat 35 642 649 657 664 671 679 686 693 695 700 707 715 722 790 36 632 699 646 653 660 668 675 G2 Ged GA 596 703 7.11 7:18 37 622 628 698 643 650 657 664 671 673 678 685 692 700 707 612 618 625 633 640 646 653 661 663 668 674 Ger GAD 695 602 609 616 623 620 638 643 650 652 657 664 671 678 685 593 699 606 613 620 626 693 640 642 647 653 660 668 674 583 590 597 603 610 616 623 630 622 637 643 650 657 664 574 580 587 $94 600 606 613 620 622 627 633 640 647 653 564 S71 578 584 S81 597 604 610 615 617 624 690 6a7 643 555 561 568 575 582 588 594 601 603 608 614 620 627 633 546 559 559 565 572 579 585 S81 594 598 605 611 6:17 6.24 598 544 550 557 563 569 576 582 5B 589 595 601 608 614 529 595 541 $43 S54 560 567 573 575 579 586 S92 598 6.05 520 526 592 539 S45 581 S57 564 566 570 575 58a SB9 5.95 512 518 524 590 596 542 549 555 557 561 567 574 580 5.86 503 509 515 S21 527 533 540 546 548 552 558 564 570 5.77 8 se455 £6625 BB 29 Centennial Road, Orangeville, ON, L9W IRI (519) 941-8161 Fax: (519) 941-8164 loa tee penne 118 CONTROLS