You dont have to like chemistry, but you have to respect it

Posted on September 9, 2013 by Team CCJ

Cycle chemistry demands particularly close attention for units experiencing weekday starts and weekend (or longer) shutdowns. Attendees at the last meeting of the Australasian HRSG Users Group were polled regarding their two-shifting experience (shutdowns of four to six hours) and what return-to-service/standby chemistry issues they were facing (if any). One user said his 175-MW plant was designed for base-load service but had been two-shifting/peak-chasing the last five years. The 2 x 1 station has only one HRSG and it is of the once-through design. Thus its optimal cycle chemistry is different from that used in drum-type boilers. However, this plant also was dealing with chemistry issues and had suffered stress corrosion cracking in the steamer. One of the worlds leading powerplant chemists reminded the group of the two basic rules for two-shifting: 1. Dont allow the redox potential to change. In case youve forgotten what this term means, redox, or oxidation reduction potential (ORP), is a measure of the nature and strength of an aqueous environment in millivolts (positive when oxidizing, negative when reducing). 2. If using an oxidizing cycle, dont change pHthis to minimize the amount of corrosion-product transport. Its all about the interfacial science, he said. You want to maintain the oxide in a stable condition. Another chemist suggested holding vacuum between the operating cycles if possible and to run makeup water through a membrane degasser to minimize its oxygen content. The first chemist added that users should not worry about CO2 ingress. AVT(O). An attendee wanting a better understanding of how all-volatile treatment (oxidizing) works asked: Do you just run with no reducing agent and rely on air ingress (which may be very minimal) or should you have oxygen injection? One of the top chemists responded. It does not matter, he said; the original concept for AVT(O) was to make it different compared to AVT(R, reducing)specifically, eliminate the use of a destructive reducing agent. However, experience with AVT(O) has shown that very low oxygen levelsthat is, less than 5 ppb at the condensate pump dischargeis not optimal. Ideally, the consultant continued, you want about 10 ppb at that point in the system, from air or oxygen. He also suggested that users monitor system health by checking drum oxide color (red is good) and ensuring

that all surfaces touched by water are passivatedthis to obtain a hematite dominated film. Another chemist in the room said it was his experience that some plants admit air on the vacuum side of the condensate pump, others inject oxygen manually or via automatic control. He suggested that some valve tweakers may pose risks if manual adjustment of oxygen content is employed. An automatic injection system is better, the chemist said. There was considerable give-and-take on the subject. One user offered that in switching coal-fired units from AVT(R) to oxygenated treatment in the early 1990s, plant personnel found there was insufficient oxidizing power with AVT(O) and air was added. No issues. An OEM representative remarked that for units with an LP-drum feedwater tank system, CO2 ingress will give high cation conductivity (CACE, for conductivity after cation exchange) in LP steam and that this causes confusion as to whether carryover is occurring or not. The chemists responded. One said CO2 is not an issue; you have to understand what is causing the elevated CACE. Another suggested testing carryover using ion chromatography (IC) to get at the root cause of the problem. But if you do this, he said, be sure you know if youre sampling saturated or superheated steam. A user then commented that OEMs give chemistry specifications for steam, but IC analysis conducted to determine the reason for high readings of cation conductivity at his plant showed no issues with sulfate or chloride so they continued to operate. Another user in the audience held up the caution flag regarding operation outside of OEM limits. A recent steam-turbine failure, he said, illustrated the importance of documenting such operational decisions. You need to put in an official record the justification for not running within OEM limits in case a legal issue develops in the future. Mention was made of ongoing work by the International Association for the Properties of Water and Steam (IAPWS) that would soon provide users validated guidance on issues discussed during the foregoing exchange. Stay tuned for developments. Chemical cleaning is a subject about which relatively little has been written regarding HRSGs. An attendee asked: Whats the best chemical for cleaning the steam/water side of HRSGsinorganic acid (such as HCL and HF) or organic acid (citric or formic)? Are boil-out, flushing, and steam/air blowing alternatives? There was no clarification as to whether the question pertained to a precommissioning chemical clean or one required by poor operating

practices over the years. Most in the group offering an opinion assumed the former, judging from their comments. An OEM engineer said the choice of cleaning solvent often depends on environmental disposal options and cost, adding that a degrease stage might not be so necessary today. That almost certainly would be the case for a unit that had a service history. A user said it was necessary to do a full clean rather than just a degrease, which most respondents apparently agreed with. Another OEM engineer said decisions on chemical cleaning normally are made by the EPC contractor. That likely would be the case in the US, but not necessarily the way things are done elsewhere. A chemist with deep knowledge said solvent selection is site- and project-specific, the former impacting accessibility of chemicals and waste disposal. Experience in Australia and New Zealand, he said, has been with citric acid, HF, and HCl. Of great importance, the chemist added, is a detailed specification that defines the scope (Is the full steam path included?), various steps in the processsuch as flushing, iron removal stage, passivation stage, flush, and storageand the metrics for determining when the unit is considered clean. The discussion dug deeper with an OEM engineer mentioning that superheater cleaning often is avoided in the US because of chromium disposal concerns. Regarding the waste stream from the cleaning of evaporator panels made of steel containing small amounts of chromium, he was unaware of any issues. Yet another HRSG supplier was said to have identified no issues associated with the cleaning of T91 superheaters. A second chemist joined the information exchange noting there may be risks associated with cleaning the superheaters of future plants because of unknowns associated with the effects of solvents and inhibitors on advanced materials. While the conversation seemed to support the notion that less might be more with regard to chemical cleaning, a naysayer took the floor citing under-deposit corrosion failures in the preheater sections of one unit that was not cleaned after construction 10 years earlier. One of the two most vocal chemists said its not unusual to find heavy deposits in preheaters and he didnt see that as a general problemunless the deposits were super heavy, as no boiling should occur in the preheater. This is unlike the condition in an evaporator, where concentration mechanisms are conducive to under-deposit corrosion with heavy tube deposits and poor water chemistry.

The subject of air blows versus steam was the next topic. A user said he preferred steam because of the poor performance experienced with air blows. An OEM reported good experience with air blows, with no operational issues identified after commissioning. There are many different variations of steam blows, a consultant noted: continuous blow, intermittent blasts, low pressure, high velocity, etc. However, no advice was offered on what was most effective and under what conditions. When planning for boiler cleaning, the group was told, be sure to have plenty of makeup water available in temporary tankage onsite. Supply often is the limiting factor for steam blows. To sample tubes, or not? Practical questions and insightful discussion are a hallmark of AHUG. What are people doing in regards to HP evaporator tubes: sample or borescope inspection? Very difficult to justify engineering to allow for tube sampling was the first reply, from a user. Another owner/operator said his company has taken HP evaporator tube samples from all units in its fleet. First time was in 2010 after a base-load plant had operated for 10 years. Samples were taken high up and to the sides; duct burners are in the center of the tube bundle. A consultant said discussion on the subject at another user group meeting suggested that the heaviest deposits might not be found high up in the tube. Another user apparently agreed. It sampled two tubes in one unit, the first tube center and top, second tube sample center and side. No issues were identified. Yet another owner experienced several evaporator-tube failures and its consultant reported lots of variability in tube condition. It was moving towards use of a borescope to identify areas of concern. A chemist questioned this looming decision. He considered it risky, saying you typically find during a proper analysis that which you see bears no relationship to the results from a scanning electron microscopethe information needed to determine when to clean a boiler.