Dedicated Online Analyzers for Power Plants Primary Circuit Water-steam Circuit Cooling Water Circuit Waste Water DM Water Plant Makeup Water Raw/Ground Water Monitoring and Protecting against Corrosion Power Plants & Corrosion Nearly 50% of unplanned downtime in power plants is Boiler Operators (formal y known as VGB – Vereinigung caused by contaminants or problems in the chemistry of der Grosskesselbesitzer e.V.), the European Power Plant the water-steam circuit, with corrosion being the primary Suppliers’ Association (EPPSA), and the International As - 02 factor. Corrosion chemistry monitoring helps to minimize so ciation for the Properties of Water and Steam (IAPWS). loss of efficiency and protect the components coming Nuclear power generation is governed by the safety in contact with steam and water against damage. The standards of the Nuclear Regulatory Commission (NRC) mechanisms and associated root causes responsible for and the International Atomic Energy Agency (IAEA). most chemistry-related damage and efficiency loss are now very well understood, but the precise conditions Every cooling circuit has a unique design and thus its at which corrosion and deposition activity begin are own unique chal enges. The specifics of the water che - still not known. Past and present chemistry guidelines mis try to be regulated (and therefore the applicable all serve to provide the operator with a warning as to limits) depend on the type of power plant, the cooling when corrosion and/or deposition activities that place circuit design, and construction materials. the power generation unit at risk may begin. Timely and effective monitoring of power plant water Various guidelines define the permissible operating chemistry is critical for maintaining efficiency and saf e ty. ran ges for water chemistry used by power plant ope-By using online analyzers, operators gain the infor ma-ra tors, including standards provided by the Electric tion they need to accurately identify trends and address Power Research Institute (EPRI), the Association of Large operational issues before costly problems arise. Dedicated Online Analyzers Effective cycle chemistry programs depend upon the Metrohm Process Analytics offers integrated online selection of treatments customized to the specific unit and analytical systems based on lab-proven methods in tit ra-its characteristics. Treatment control and optimization, tion, spectroscopy, electrochemistry, photometry, TOC, in turn, requires rapid, accurate sampling and analytical ion chromatography, and ion selective mea sure ments. capabilities. While all power plants can benefit from These application-specific solutions utilize optimized online analysis of critical parameters such as corrosion sample conditioning to bring precision and accuracy indicators and inhibitors for optimum chemistry control, to effective power plant chemistry monitoring. This monitoring of diagnostic parameters such as chloride, product line leverages Metrohm Applikon’s expertise in sodium, sulfate, ammonia, hydrazine, silica and TOC can online analysis and the know-how of the world leader in also be highly advantageous for protection and process ion analysis, Metrohm AG, to bring laboratory analysis optimization. Not only do dedicated online analyzers online for excel ence in continuous monitoring and con - help to safeguard plant operation and efficiency, but trol. they also provide a continuous record of plant operating conditions for increased plant uptime and to facilitate long-term improvements in productivity. Flow-Accelerated Corrosion Monitoring Flow-accelerated corrosion (FAC) of the metal com - sulfate, it also leads to corrosion fatigue and stress cor - ponents in power plant water-steam circuits reduces ro sion cracking (SCC). To prevent these detrimental the lifetime of water-exposed carbon steel pipework ef fects, power plants have to monitor these anions in and copper heat exchangers. Zinc ions, phosphates, the water-steam circuit to trace levels. Corrosive ions and phosphonates are commonly used as corrosion and the corrosion inhibitors can be monitored by ion inhibitors in steel piping. Chloride causes pitting corro-chromatography. sion on turbine blades and rotors. In combination with Process Ion Chromatograph The new Process Ion Chromatograph (IC) is designed for 03 autonomous operation with absolute reliability, based on our decades of experience as a leader in this analytical technique. The Process IC al ows multicomponent analysis from a single sample stream, providing important information about any corrosion event. The Process IC measures multiple anions and/or cations simultaneously, and offers further measurement options including monitoring multiple sample streams, corrosive ions, dissolved Purpose Corrosion monitoring & control, metals, and corrosion inhibitors. Providing quick, reliable increased infrastructure lifetime results, this system gives valuable insight into the status Application Online monitoring of corrosive ions of corrosion processes within a plant by continuous and corrosion inhibitors comparison of results with control values. By correlating Technology Ion Chromatography the results with specific events, effective corrective ac - Concentration ng/L to % tion can quickly be undertaken to prevent or minimize Range plant downtime. Sampling Metrohm Inline Sample Preparation (MISP) Analysis time Application-dependent, typical y 10–45 minutes Nuclear Power Plants The most common types of nuclear reactors are the Fuel assemblies cannot be exchanged during operation boiling water reactor (BWR) and the pressurized water of a PWR due to their use of light water, so a fuel re - reactor (PWR). The primary circuit of a PWR circulates serve must be in place prior to the start of an operating cooling water at high pressure (up to 160 bar) through cycle. The associated excess activity in the reactor is the reactor core, where boric acid dissolved in the pri - con trol ed by using a higher boric acid concentration. mary circuit acts as a moderator for the nuclear reac-As the fuel decays, the boric acid level is lowered to tion. Determination of boric acid concentration in the maximize reactor output, achieved via dilution with primary circuit is thus extremely important in control ing ultra pure water. From one refueling to the next, boric reactivity for reactor efficiency and safety. acid concentration fluctuates from 2,000 mg/L to zero, and thus online monitoring of boric acid concentration in the primary circuit is extremely important for efficient and reliable operation. Main Steam Steam Turbine Isolation Valve Generator Steam Reactor Containment Steam Control Rods Generator Cooling Water Return Condenser team essel Reheat S Reactor V Reactor Collant Pump (Internal) Main Feedwater Steam Isolation Valve Generator Reactor Collant Feed Pump Condensate Pump (External) Condenser Cooling Pump Cooling Tower Water Pump Valve Feedwater Heater Boric Acid Analyzer Uranium Analyzer The Boric Acid Process Analyzer provides fast and 04 Control and treatment of liquid effluents are required reliable values via potentiometric titration for continuous throughout uranium mining and processing for effective monitoring of boric acid concentration throughout the environmental protection. Effluent water from nuclear fuel cycle, both during the process and in the spent fuel power plants must also be monitored to ensure residual pool. Use of an automated titration system eliminates uranium concentration is within regulated limits. The the tedious pipetting of the sample, distil ed water, and Uranium Analyzer accurately determines uranium con-mannitol solution needed for boric acid determination centration in various water cycles and in waste water through manual methods. Automated analysis improves streams. Based on colorimetric measurement and avail-accuracy, eliminates the potential for operator error, able in both basic and advanced configurations, these and provides more rapid process feedback to maximize systems provide sensitive detection of trace uranium operational efficiency. concentrations. By integrating this online system into a plant, reporting of out-of-limit uranium can be made Purpose Safe operation both rapidly and accurately. Application Online monitoring of boric acid concentration Purpose Environmental protection Technology Potentiometric titration Application Online monitoring of uranium in Concentration 0–6 000 mg/L boron water cycles and in waste water Range Technology Colorimetric measurement Sampling Fixed volume burette Concentration 0–100 mg/L uranium Analysis time 1–15 minutes Range Enclosure NEMA 4/IP66 standard, Class 1, Sampling Constant Div. 2 enclosure optional Analysis time 10 minutes Fossil Power Plants Fossil power plants consume fuel such as coal, natural gas, or oil, generating electricity via a steam turbine. The steam generation process requires cooling water, either in a closed loop or open loop system, so that the steam can be condensed for either re-use or discharge depending on the type of system. Cooling water composition must be monitored to optimize power generation, ensuring plant efficiency and safety. Additional y, exhaust gases containing carbon dioxide and sulfur dioxide produced during the power generation process must be treated prior to release to the environment. Monitoring of the flue gas treatment process is required both for plant efficiency and to ensure environmental compliance. Metrohm Process Analytics offers process analyzers based on tried and true laboratory methods for each of these applications to ensure safety, productivity, and environmental protection. Flue gas Desulfurization Plant The flue-gas desulfurization (FGD) process is used during the incineration of waste materials – one of the steps in the process to remove species that are deemed harmful to the environment. FGD is a wel -established process technology in fossil-fuel power plant operations. Calcium Analyzer Flue gas is treated with an alkali to remove sulfur dioxide, 05 typical y using calcium hydroxide, or less frequently mag nesium hydroxide, both of which react within the sul fur reduction process with sulfate and neutralize the acid content and precipitate as FGD-gypsum. One of the final products of the neutralization and reduction process is sulfate, which in turn will form calcium sulfate, or magnesium sulfate. The Metrohm Process Analytics Cal cium Analyzer is based on both potentiometric and thermometric titration techniques, and is used to mea - sure both the calcium hydroxide and sulfate content in several stages of the scrubbing process. By utilizing these online measurement approaches, the efficiency of the Purpose Environmental protection and scrubber can be optimized for process performance and process efficiency scale formation can be prevented, resulting in reduced Application Online monitoring of calcium operational and maintenance costs. hydroxide Technology Potentiometric and thermometric titration Concentration Ca2+ 0–40 g/L: SO 2- 0–100 g/L 4 Range Sampling Filtration to remove solids Analysis time 10–15 minutes Benefits of Metrohm Process Analyzers • Process analyzers that provide automated analysis results • Analytics based on industry standard lab methods • Optimized sample conditioning for automated and reliable operation • Easily transfer lab methods online to reduce method bias • Rapid, accurate results maximize safety, efficiency and Thermal Power Plant Waste Collection Flue-ash Gypsum Furnace Flue-gas Scrubber Carbon Capture Analyzer Nitrogen Species Analyzer When flue gas is treated with a scrubbing solution, Ammonia is added to cooling water streams to help main-06 aci dic CO is reversibly chemical y bound by amines in tain a slightly basic pH, thus slowing corrosion. Other 2 the solution, after which it is released by heating and nit rogen containing corrosion inhibitors such as azoles then compressed, dried, and liquefied. After the amine-are sometimes used, which can degrade to produce nit-containing scrubbing solution has been cleaned by ro gen species such as ammonia, nitrite, and nitrate in counter flowing steam, it is cooled and recycled back into water streams. Monitoring of many nitrogen species is the process. The Carbon Capture Analyzer determines required prior to water and waste water discharge to the CO binding capacity of the scrubbing solution that ensure environmental compliance. While a more basic 2 is required to completely remove the CO in the flue gas nitrogen analyzer can be used for monitoring a specific 2 from measured bound and free CO concentrations in nitrogen species such as ammonia, the Nitrogen Species 2 the scrubbing solution. Analyzer delivers rapid, accurate measurements of am - mo nia, nitrite, and nitrate species simultaneously, and A single Carbon Capture Analyzer can monitor several can be configured to handle multiple streams. sample streams and determine the CO binding capa-2 city of several amine scrubbers in succession. By im ple - Analysis time 10 minutes menting Metrohm’s ful y automated online mo ni to ring Purpose Corrosion prevention and solution for this process, it is possible to optimize the environmental protection amine activity and measure the efficiency of the CO Application Online monitoring of ammonia 2 capture, reducing overall costs while ensuring en vi ron-and other nitrogen species men tal compliance for CO emissions. Technology Ion-selective electrode or colorimetry 2 Concentration Ammonia: 0.15–50 mg/L by Purpose Process efficiency and environmental Range ISE (other ranges possible) or protection 0.003–3 mg/L by colorimetric Application Online monitoring of CO binding method, Nitrite: 0–5 mg/L by 2 and amine concentration colorimetric method, Nitrate: Technology Potentiometric titration 0–20 mg/L by colorimetric method Concentration 0–100% CO , 0–100% amine Sampling Filtration 2 Range Analysis time 10 minutes Sampling Filtration, density – used for concentration determination Analysis time 15–20 minutes Cooling Water Cycle Cooling water is used to condense the exhaust steam from the turbine to water, traveling through kilometers of piping in the condenser before being sent back to the water-steam circuit as feed water. The cooling water itself is cooled either by once-through cooling, in which heat is transferred to water taken from a river, or in a circuit in a wet cooling tower via heat dissipation into the atmosphere. Continuous circulation of the cooling water in either system increases the concentration of contaminants, and requires water analysis to control cor rosion and deposition processes taking place in the cooling water circuit. Metrohm Process Analytics online process analyzers provide sensitive and reliable determination of contaminants at the low concentrations present in cooling water to enable rapid feedback and corrective action. 07 Silica Analyzer Phosphate Analyzer Buildup of silica from boiler feed and cooling water Trisodium phosphate is used for corrosion prevention can lead to reduced boiler efficiency and eventual y in boiler water systems, leading to the need to monitor blockage and rupture of pipes. Monitoring of the silica phosphate levels at several points within the process. content in influent and cooling water can provide Phosphate levels are ideal y kept low to prevent any valuable information that is useful in preventing scaling precipitation and solids transport, yet must remain high and operational efficiency losses. The Metrohm Process enough for corrosion prevention. The phosphate used Analytics Silica Analyzer can monitor silica levels from low for this purpose can sometimes be carried over into ppb to high ppm level, which is critical for maintaining other systems, particularly the steam system, leading to the required low levels of silica and preventing costly similar precipitation and scaling issues. scaling and related issues. Purpose Scaling prevention Purpose Corrosion prevention, scaling Application Online monitoring of silica prevention, and environmental Technology Colorimetry compliance Concentration Range 0–1 mg/L silica Application Online monitoring of free phosphate Sampling Filtration Technology Colorimetry Analysis time 10 minutes Concentration 0.01–0.5 mg P/L Range Sampling Filtration Analysis time 10 minutes www.metrohm.com erisau 0 H -910H , CG hm A etro y M itzerland bw n S rinted i, p SW ch A ns -12 016 dificatioo N – 2 cknauer+Scho o m y E 22E ut b 0.520.0 Subject t Layo 8