Performance Monitoring in the Water Treatment of HRSGs

A Banweg, Nalco Chemical Co. IWC 99-14

KEYWORDS: heat recovery steam generator, water chemistry, corrosion, deposition, monitoring. Summary: There are a wide variety of HRSG designs in operation today. In addition they can vary in service from a pure electric utility generator to one that may be integrated into an industrial manufacturing process. To obtain maximum efficiency in extracting the waste heat energy in these systems, these multiple pressure level steam generators can be highly integrated. This level of integration and the physical arrangement due to the low heat fluxes, make some traditional performance monitoring technology difficult to apply. The proper selection and application of water chemistry monitoring and performance monitoring is required to treat these systems.

Introduction One of the more common types of steam generating systems currently being installed in both utility service as well as in industrial cogeneration facilities is the heat recovery steam generator, HRSG. These systems are generally configured to absorb the waste heat from the exhaust of a combustion gas turbine (1) Fig. 1. These systems have heat rate and efficiency advantages over conventional fired steam generators. In the industrial situation, they offer the same efficiency advantage, with capacity that is compatible with many industrial cogeneration requirements. The details on unit design can vary substantially but functionally are very similar to conventional fired steam generator component designs; natural circulation and forced circulation drum type boilers and once through designs.

deaerator in a system to the intermediate pressure, IP and high pressure, HP sections in the multiple pressure design. HP boiler design pressure may be as high as 2000 psig Fig. 2(2). For electric utility service that system may also include a reheater.

Boiler Designs HRSG boiler designs range from simple single pressure, natural circulation drum type boiler designs, Fig. 1, to forced circulation, once through boiler designs. The tubing configuration can be either horizontal or vertical in orientation. For the most part, other than one type of once through boiler design, which uses Inconel as the evaporator tubing material, and the incorporation of a stainless steel preheater, prior to the economizer in some designs, the materials used are the common ASME materials that are used in conventional fired boiler designs. HRSG designs range in design pressure, from the low pressure, LP, boiler design pressure in a multiple pressure design that might be 5-10 psig, operating primarily as the Fig. 1 Simplified Combined Cycle System

boiler heat transfer surfaces, while maintaining the design steam purity limitations. The configuration of a particular boiler system may limit treatment choices. In the multiple pressure HRSG system shown in Fig. 2, where the low pressure boiler acts as a deaerator and is the source of feedwater and spray attemperator water for the IP and HP boiler, all volatile treatment (AVT), is required. The operating history (3) of these units as well as some theoretical modeling done on the solubility of magnetite (4) under low pressure AVT chemistry, shows that this is not the ideal chemistry to apply, even though required by the application. This modeling demonstrates much lower magnetite solubility and therefore much better protection using solid alkali treatment in these low-pressure systems when compared to all volatile treatment. Unless another source of spray attemperator water is found though, this treatment cannot be changed. Additionally there may be restrictions on the use of volatile alkalizing materials such as neutralizing amines, due to the end use of the steam in some industrial or district heating applications as well as a restriction on the particular chemical content of the steam produced. Some industrial steam applications may wholly prohibit the use of nitrogen or sulfur based treatment compounds in the steam. The type of service that a particular HRSG is used in must also be factored into the treatment chemistry choice. It is critical also in the formulation of system monitoring and contingencies for out of specification chemistry conditions. In a pure electric utility service role, the EPRI guidelines previously developed for fired utility boiler applications are directly applicable to the appropriate HRSG boiler configuration. These will soon be published as Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators (2). The availability of these guidelines though, is limited and costly to the general non-utility operator. In electric utility service these HRSG systems tend to be the higher operating pressure systems, with very low make up water requirements and conversely very high condensate return percentages, simple condensate systems, and cooling water contamination of the condensate as a primary concern. As in any high pressure utility situation the primary concerns are condenser leaks and the potential for hydrogen damage or other under deposit corrosion, phosphate hide-out and the potential for acid phosphate wastage, air inleakage and out of service protection. Merchant power applications for HRSGs in the utility

Fig. 2 Natural circulation multiple pressure HRSG The most common design seems to be drum type, natural circulation type boilers, with vertical evaporator tubing. Since convection is the primary mode of heat transfer in these systems, from relatively low temperature exhaust gas, externally finned tubing is common in most of the heat absorbing components, economizer, evaporator, superheater and reheater, with very close tube spacing in the gas pass. Once through type boilers tend to have horizontal tube orientation as do the forced circulation drum type units. Water chemistry Because of the wide range of design pressure conditions and boiler configurations, all the common types of water treatment chemistry may have application. For drum type boiler systems, internal treatment chemistries may range from all polymer treatment technology for the lowpressure softened make-up water systems to equilibrium phosphate chemistry for the high-pressure very high purity make-up water systems. The once through design restricts the water chemistry to all volatile treatment (AVT) chemistry. Oxygenated treatment can have application in this boiler configuration, if the materials of construction of the feedwater system are appropriate and the required feedwater purity, <0.15 microSiemens/cm is continually maintained. Many of these once through systems though do not incorporate a full flow mixed bed condensate polishing system.Drum type boiler make-up water purification can range from zeolite softened to reverse osmosis and mixed bed demineralization, depending on the steam purity requirements and design pressure. The goals in water treatment in these HRSG systems are the same as in conventional boiler systems; corrosion control in all parts of the system, deposition control in the

industry may require additional chemical feed system changes to address this industrys transient load pattern of requiring power at very short notice, and therefore chemical treatment in much shorter demand times, than what is normally required for steady state operation. This type of service will also require consistent lay up practices for out of service protection. Today there is a very good understanding of the types of boiler tube failures that systems are prone to as well as their root causes and corrective actions in both the electric utility environment(5) as well as the industrial operating environment(6). When the service life of an HRSG is in an industrial cogeneration type of environment, a much wider scope of parameters must be examined to evaluate the most appropriate chemistry to use, monitoring to be done and corrective actions to be taken when out of specification chemistry conditions occur. Since there is such a wide variation of HRSG system design, and industrial applications also vary widely, this must be done on a case by case basis. In an industrial system the percent make up for a system may be up to 100%. The ASME guidelines (7) address industrial applications that can have softened water make-up as well as higher degrees of make-up water purity. Condensate can be a combination of hotwell condensate as well as process condensate. This process condensate can contain a variety of contaminants other than cooling water; hydrocarbons, organic acids, soy oil, freon, black liquor etc. Provisions must be made in grab sampling and on line analysis, for the timely detection of these contaminants and appropriate corrective actions to be taken. Steam Purity The steam produced can have a number of end uses in these HRSG applications in addition to driving the steam turbine generator. The steam can be used for NOx control in the gas turbine, as the cooling medium for the gas turbine component (8), and as export steam to a steam host/user. Each of these uses imposes specific steam purity restrictions: NOx control Steam turbine GT cooling 30 ppb Na+K+L 10 ppb Na 1 ppb Na

(9)

are required to properly sample saturated steam. It is much more desirable to have the ability and to measure and assure the steam purity of both HP and IP steam prior to any component failure. As an additional note of caution, when the internal treatment chemicals that are used for the alkalinity source or the phosphate source are based on potassium compounds, then the traditional approach of measuring steam purity by measuring the sodium content of the steam with a sodium selective ion electrode, will not accurately reflect the steam purity and may significantly under report the steam purity level. These restrictions on steam purity tend to dictate very strict make-up water purity in the design of most of these systems. Mixed bed demineralized water with a conductivity <0.5 microSiemens/cm is quite common, even for drum type boiler systems. Flow Accelerated Corrosion Flow accelerated corrosion (FAC), has been a topic of concern in both utility and industrial applications (10). It is also a serious concern for these HRSG systems and must be accounted for in the treatment chemistry. HRSGs are affected by both single phase flow FAC as well as two phase flow FAC. Single phase flow FAC is a concern in the feedwater systems including any preheaters, feedwater heaters and economizer, both intermediate pressure and high pressure if the feedwater temperature is appropriate. Two phase flow FAC (11) is a concern for primarily the LP boiler systems of the HRSG, though some IP boilers have been affected. The use of high purity water, in such low pressure boiler systems is somewhat unique to HRSG systems. In addition the water temperature puts the carbon steel piping in a situation where there is a very high solubility potential of iron in water, Fig. 3.

As in fired boiler systems, it is mandatory to have the ability to properly sample steam in these systems to monitor and assure the appropriate steam purity is maintained. Properly located isokinetic sampling nozzles

monitoring of iron has been long recognized as a difficult prospect. This is because much of iron oxide corrosion products are in an insoluble state, and most water sampling systems are not designed to take a representative sample of water with respect to its suspended solids content. Significant sampling system modifications were made to the six units that were a part of the EPRI cycle chemistry monitoring project (15) to address this deficiency. Therefore the interpretation of the total iron content of a sample, in most systems has always been somewhat suspect. Laboratory and field studies have shown that when the sample is properly handled, the soluble ferrous iron (Fe+2) content of such a sample can provide some valuable information (16). Even though FAC is a very localized mechanism we have been able to measure significant increases in feedwater soluble ferrous iron content in systems known to be experiencing FAC, across that systems economizer. Chemistry variables can then be optimized to minimize this soluble ferrous iron concentration, to the extent possible in that system. Recirculating drum type boilers have an inherent inability to transport suspended solid contaminants that have entered in the feedwater out of the boiler in the continuous blowdown (CBD). Hence the reason for limitations on corrosion product contaminant levels in the feedwater (7) and no such specifications on the boiler water. When continuous blowdown cascades from the HP boiler into the IP boiler in an HRSG system, suspended solid accumulation becomes even more of a concern. Each boilers continuous blowdown system design has a maximum suspended solid removal capacity depending on the internal circulating flow geometry relative to the CBD flow geometry, and in almost all cases it is much less than 100%. The soluble ferrous iron test can also be used to optimize the ability of using the CBDs suspended contaminant removal without generating an internal FAC situation within the boiler, by the over application of treatment chemicals, such as chelants, polymers, or dispersants (16). This ability to measure soluble ferrous iron, Fe+2, also allows the detection of two-phase flow FAC in HRSG LP and IP boiler systems.

Fig. 3 Solubility of magnetite in water with ammonia(12) This situation makes it more difficult to form and maintain the protective magnetite coating on the carbon steel components necessary to protect these components from corrosion. This topic has been addressed quite well for utility boiler applications (13). For utility applications, in all steel feedwater systems, with very high purity feedwater, elevating the feedwater pH and allowing slightly oxidizing conditions appears to help. Predictive correlation (14) based on laboratory FAC data can be used to quantify the effects of chemistry options. One thing that is apparent from this correlation is that chemistry changes may have some beneficial effect but are not predicted to eliminate the FAC potential. Only a material substitution to a low chrome alloy is predicted to eliminate the FAC potential. The substitution of affected components with 12 chrome materials has been quite successful in arresting known FAC, and type 430 stainless steel, used in preheaters, seems to be immune to FAC. The available chemistry options to minimize the potential for FAC in industrial systems is substantially limited as compared to utility systems. Generally the feedwater purity is not as good or not as consistent as in the typical electric utility situation. Full flow condensate polishing systems are generally not installed, and the use of phosphate internal treatment chemistry generally restricts the use of any oxidizing chemistry philosophy, due to boiler water cation conductivity limitations to mitigate the potential for corrosion fatigue damage to the boiler. Monitoring Iron Since we are trying to protect carbon steel systems it would seem reasonable to monitor the iron content of such a system to asses the degree of success. The sampling and

chemistry with respect to corrosion control and deposition control in an iron based system. This performance monitoring technique avoids the sampling pitfalls and directly addresses the goal of the treatment chemistry. Chemical Cleaning Though these HRSG designs have relatively low heat fluxes, with time their heat transfer surfaces will accumulate waterside deposits, that may require periodic chemical cleaning. These boiler systems tend to be operated at very high cycles of concentration in the boiler water, many times at less than 1% blowdown, especially in dedicated electric utility type service. Some system designs may also cascade the continuous blowdown from the HP boiler into the IP boiler. Both, situations that will tend to further foster deposit accumulation of the typical metal oxide feedwater contaminants, on the heat transfer surfaces of the boiler. Because of their low heat flux of operation HRSGs would be expected to be able to tolerate higher level of deposit accumulation than a fired boiler of the same pressure, prior to experiencing under deposit corrosion problems. Though not as prone to overheating type boiler tube failures as a fired boiler, HRSGs are susceptible to under deposit corrosion damage. Where a typical recommendation for a conventional fired boiler would be to take tube samples and determine whether cleaning is required, this is very difficult in the closely packed, finned tube geometry of typical HRSG designs (18). Additionally there are no published deposit weight chemical cleaning criteria specific to HRSG designs. Even in conventional boiler designs there may be significant variations in tube deposit weights in adjacent tubes even in the high heat flux area. The low heat fluxes in HRSGs, and low velocities, may lead to significant additional deposit accumulation in low flow areas. Periodic hydrogen studies of the saturated steam have been used for many years in fired boiler systems to assess the need to chemically clean (19). Hydrogen measurement detects the under deposit corrosion activity possible when deposits accumulate on heat transfer surfaces to the point of being able to generate a concentrating mechanism sufficient to raise bulk boiler water concentrations to corrosive levels under deposit. With the difficulties associated with being able to take tube samples from most HRSGs, periodic hydrogen analysis of saturated steam would be a better performance monitor to determine cleaning frequency. Conclusion There are many aspects of the operation and design that are unique to HRSGs but there are also a number of

Fig. 4 Iron in Boiler Blowdown An important consideration in this type of optimization is an accurate knowledge of the cycles of concentration or conversely the continuous blowdown rate that the boiler is operating at. This is difficult to determine by classical methods in high purity boiler water systems where amines are used for condensate treatment. The feedwater versus boiler water conductivity relationship, for example, in this situation may grossly under predict the cycles of concentration because of the amines relative volatility at steam drum conditions. The measurement of other trace contaminants also becomes difficult/inaccurate at their low feedwater concentrations. Nalcos patented TRASAR technology offers a very reliable tool to accurately determine cycles of concentration (17) in boilers up to 1500 psig operating pressures either diagnostically or as an on-line chemical control means.

Fig. 5 Cycles of concentration by TRASAR Accurate cycles determination and the evaluation of soluble ferrous iron versus total iron concentration are necessary to properly evaluate the behavior of treatment

commonalties to fired boiler design experience and treatment that allow us to use the appropriate performance monitoring techniques already developed: 1.) Chemistry optimization through monitoring the soluble ferrous iron content of feedwater and boiler water. 2.) Deposit accumulation evaluation by periodic measurement of the saturated steam hydrogen content. 3.) Accurate cycles of concentration monitoring and control using TRASAR technology. REFERENCES: 1.) STEAM, its generation and use, pp. 31-1, 31-4, Babcock & Wilcox, .40th edition 2.) Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators, TR-110051, Electric Power Research Institute, copyright 1998 3.) Stanley, L., Troubleshooting HRSG Problems, Power, July/Aug. 1996 Corrosion

4.) Bursik,A., Jensen, J.P., Staudt, U., A Look Behind the Boiler Water Treatment Guidelines, Comments on Present and Possible Future Practice, IWC 96-32 5.) Manual for Investigation and Correction of Boiler Tube Failures, CS-3945, EPRI 6.) Port, R.D., Herro, H.M., Nalco Guide to Boiler Tube Failures Analysis, McGraw-Hill, 1991

7.) Consensus on Operating Practice for the Control of Feedwater and Boiler Water Chemistry in Modern Industrial Boilers, American Society of Mechanical Engineers, 345 E. 47th St., New York, 1994 8.) Donovan, J., Bellows, J.C., The Ultrapure Steam Cycle, International Joint Power Generation Conference, Burlingame, CA. 1999 9.) ASTM, Standard Practice for Sampling Steam, D1066 10.) Tvedt, T., Chagnard, H., Pathology of Single Phase Flow Assisted Corrosion in Industrial Boilers, IWC 97-56 11.) Port, R., Flow Accelerated Corrosion, NACE Corrosion 98, paper#721 12.) Sturla, P. VGB Kraftwerkstechnik 3, pp. 231-239, 1979 13.) Flow Accelerated Corrosion in Power Plants, TR106611-R1, EPRI 14.) Erosion Corrosion in Power Plants, Single & Two Phase Flow, Experience, Prediction, NDE, Maintenance and Remedial Measures, IWC 89-16 15.) EPRI RP-2712-3 Monitoring Cycle Chemistry At Six Fossil Plants, Aschoff A., Sopocy D., Stauffer, C., Dooley, R.B., IWC 86-22 16.) Godfrey, M. Chen, Y., Eisner, I.E., On-line Corrosion Monitoring in Boiler Systems, NACE Corrosion 95, paper #621 17.) Banweg, A. Avallone, S. Kuller, D. Performance Monitoring Tools for Improving the Operation, Efficiency, and Reliability of Industrial Boiler Water Systems, Watertech, Houston, TX, 1994 18.) Weick, R.H., Internal Boiler Tube Deposit Weights as a Basis for Chemical Cleaning, NACE Corrosion 94, paper #208 19.) Kelly, J., Banweg, A., Hydrogen Analysis as it Relates to Boiler Life Expectancy, NACE Corrosion 98, paper #723