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Issue 04 (2019)

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An Interlaboratory Test of Analysis Methods for Corrosion Products

Karsten Thomsen and Maja Skou Jensen

This report describes the outcome of an interlaboratory comparison of analysis methods for iron among a group of laboratories in the power and heat industry. The samples sent out to the laboratories were real samples of feedwater and district heating water that had an inherent inhomogeneity due to the particulate nature of the corrosion products. The analysis methods compared were the standard methods based on spectrophotometry and inductively coupled plasma spectroscopy as well as analysis of filtered material on a 0.45 μm membrane filter. The filtered material from a 1 L sample was digested and dissolved to a 50 mL final sample volume, which gave a concentration factor of 20, enhancing the sensitivity of the method relative to the others. The purpose of the interlaboratory comparison was twofold: to qualify the filter method to be recommended for corrosion product analysis by the International Association for the Properties of Water and Steam in a Technical Guidance Document, and to give the laboratories an opportunity to test their methods on realistic samples against a group of other professional laboratories. For accredited laboratories, proficiency testing like this is a well-known and prescribed means of quality control and often supplements the internal quality control nicely.

Although measures had been taken to minimize the heterogeneity of the samples, the district heating samples turned out to be not even close to homogeneous. By assuming a log-normal distribution and independent results of the double determinations from each laboratory, the inhomogeneity of the samples could be handled, and the performance of the laboratories compared. The comparison shows that the reproducibility of the filter method matches the reference methods, and that both feedwater and district heating water samples fit nicely to the log-normal distribution. The results indicate that the filter method is reproducible when transferred from one laboratory to another.

PowerPlant Chemistry 2019, 21(4), 218–229

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Thirty Years of Experience with Film-Forming Amines at a Norwegian Fertilizer Production Site

Roy van Lier, André de Smet, Lene-Marie Olsen, Matej Halasa, and Trond Arve Fjærem

In Glomfjord, Norway, above the Arctic Circle, Yara produces some 400 000 t (100 % equivalent) per year of nitric acid in two older units. All of the acid is used in downstream plants on site to produce a range of fertilizer grades.

The Glomfjord site has been of great importance both to the pioneering of ammonia and nitric acid synthesis technology and to the history of Norsk Hydro, which eventually divested its fertilizer activities as Yara International. It is also a location with some of the longest operational experience with film-forming amines for industrial steam system treatment, certainly in relation to nitric acid production.

The present paper first provides background information on the Glomfjord site. Steam generation in nitric acid plants in general is then succinctly explained. Yara’s operational experience is subsequently elaborated in the context of the specificities of the Glomfjord application, and of filming amine and water chemistry in the Nordic countries. This includes analysis of a possibly unique case of fouling and damage that illustrates the importance of adequate boiler feedwater quality, regardless of the chemical treatment program in place.

PowerPlant Chemistry 2019, 21(4), 232–241

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Critical Chemical Issues during Pre-commissioning

Andrés Rodríguez Pérez

Most cases of severe corrosion and consequent failure in the commercial operation of water-steam cycle and boiler systems are initiated during the first stages of a project, frequently because of a lack of preservation, an absence of regular inspections, inadequate water quality for pressure tests and a lack of understanding of corrosion processes by many of the parties involved.

Selecting an appropriate pre-commissioning program control will mitigate the risk of corrosion during the progression of the project, and subsequently, minimize potential failures upon commissioning.

Putting together an effective pre-commissioning strategy requires a great deal of coordination among different departments, the integration of practical lessons learned and great common effort throughout the project. Even engineers involved in the first stages need to retain responsibility for keeping a long-term vision for the success of the final results.

PowerPlant Chemistry 2019, 21(4), 242–249

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Issue 03 (2019)

Adsorption of Oleyl Propylenediamine on Metal Surfaces

Duygu Disci-Zayed, Julia Jasper, and Wolfgang Hater

Operation of water/steam cycles is threatened by corrosion unless proper conditioning measures are taken. As an alternative to traditional cycle chemistry, film forming amines (FFAs) are becoming increasingly important.

It is essential to understand the adsorption behavior of FFAs. This paper presents the results of an extensive study on the adsorption characteristics of FFAs on metal surfaces: stainless steel, carbon steel, copper, and aluminum alloys. Moreover, to reflect the plant conditions in a more realistic way, experiments with an iron oxide (‘magnetite’) layer were performed.

Adsorption trials were carried out with different film former concentrations and at different temperatures in a custom-made polytetrafluoroethylene vessel. The focus of this research was mainly on the use of oleyl propylenediamine (OLDA), one important FFA, which is included in the Technical Guidance Document issued by the International Association for the Properties of Water and Steam [1]. Nevertheless, other FFAs (homologues of OLDA) were also tested for comparison.

The adsorption isotherms were described with the Henry adsorption model due to the limited number of experiments and for the sake of simplicity. Adsorption of FFA accelerates with temperature and follows first order kinetics. Moreover, surface coverage by FFA was determined by mass balance, which is influenced by the nature of the metal and the FFA used.

For selected metals the surface coverage data of FFAs were compared to polarization resistance data obtained from electrochemical impedance spectroscopy. These data showed that the same degree of corrosion protection is achieved with lower amounts of OLDA compared to oleylamine (OLA).

The time dependence of surface coverage by OLDA showed the same tendency as the polarization resistance data on steel and aluminum.

PowerPlant Chemistry 2019, 21(3), 146–154

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Trends in HRSG Reliability – A 10-Year Review

Barry Dooley and Bob Anderson

By 2008 the authors had conducted assessment surveys at a small number of combined cycle/heat recovery steam generator (HRSG) plants in the areas of cycle chemistry, flowaccelerated corrosion (FAC), and thermal transients. The results clearly showed some important trends on why the major failure/damage events occurred on these plants. In the interim period the authors have extended the number of plants worldwide to 90 to allow a ten-year review of combined cycle/HRSG reliability. There has been a remarkable increase in knowledge and understanding of the main drivers of damage/failure, and in combination with the tools developed for the assessments, this paper now includes clear direction on how to address the reliability issues retroactively and how to avoid them proactively. The major cycle chemistry influenced issues are: HRSG Tube Failures due to FAC, under-deposit corrosion, deposits in high pressure (HP) evaporators, and failure in the phase-transition zone of the steam turbine. The main thermal transient aspects of thermal and corrosion fatigue relate to inappropriate/inadequate operation and maintenance of attemperators, poor drain control of superheaters and reheaters, HP drum ramp rates, and forced cooling. Another emerging issue is severe erosion of bypass pressure control valves. The paper discusses each and provides directions by which plants can avoid the issues in the future.

PowerPlant Chemistry 2019, 21(3), 158–188

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Outstanding Meetings of Two National IAPWS Committees – Press Release

The International Association for the Properties of Water and Steam (lAPWS) is the world’s leading body for power station chemistry. With AGL’s Principal Chemist Hayden Henderson being the Chairperson of the Australian branch (AUSAPWS), AGL hosted the first ever Australian AUSAPWS workshop for power station chemists in April 2019 in Melbourne.

PowerPlant Chemistry 2019, 21(3), 142

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European HRSG Forum (EHF2019) Highlights and Press Release

A hugely successful sixth annual meeting of EHF was held on the 14th – 16th May 2019 in Athens, Greece chaired by Barry Dooley of Structural Integrity. EHF2019 attracted 76 participants from 17 countries. EHF is supported by the International Association for the Properties of Water and Steam (IAPWS) and is held in association with the Australasian Boiler and HRSG Users Group (ABHUG) and the US HRSG Forum (HF).

PowerPlant Chemistry 2019, 21(3), 192–193

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