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CRTD- Vol. 35

A PRACTICAL GUIDE TO AVOIDING STEAM PURITY PROBLEMS IN THE INDUSTRIAL PLANT

AN ASME RESEARCH REPORT

prepared by the FEEDWATER QUALITY TASK GROUP

for the INDUSTRIAL SUBCOMMITTEE OF THE ASME RESEARCH AND TECHNOLOGY COMMITTEE ON WATER AND STEAM IN THERMAL POWER SYSTEMS

THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS Three Park Avenue New York, New York 10016

Statement from By-Laws: The Society shall not be responsible for statements

or

or opinions advanced in papers

printed in its publications (7.1.3)

Authorization to photocopy material for internal or personal use under circum- stance not falling within the fair use provisions of the Copyright Act is granted by ASME to libraries and other users registered with the Copyright Clearance Center (CCC) Transactional Reporting Service provided that the base fee of $4.00 per page is paid directly to the CCC, 27 Congress Street, Salem MA 01970. Requests for special permission or bulk reproduction should be addressed to the ASME

Technical Publishing Department.

ISBN No. 0-7918-1220-0

Library of Congress Catalog Number 95-80400

Copyright © 1995 by THE AMERICAN SOCIETY OF MECHANICAL ENGINEERS

All Rights Reserved Printed in U.S.A.

PREFACE

The Industrial Subcommittee of the ASME Research and Technology Committee on Water and Steam in Thermal Power Systems, under the leadership of Mr. James O. Robinson of Betz Laboratories, Inc., has pre- pared A Practical Guide to Avoiding Steam Purity Problems in the Industrial Plant. This guide was prepared by a task group of this Subcommittee under the guidance of Mr. Arthur W. Fynsk, Consultant and Mr. James O. Robinson. The task group consisted of a cross section of manufacturers, operators, and consultants involved in the fabrication and operation of in- dustrial boilers. Members of this group are listed in the acknowledge- ments. It is the plan of the ASME Research Committee to continue to review this information, and revise and reissue this document as necessary to comply with advances in technology.

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ACKNOWLEDGEMENTS

This document was prepared by the Steam Purity Task Group of the Industrial Subcommittee of the ASME Research and Technology Committee on Steam and Water in Thermal Power Systems. Recognition is hereby given to the following members of these groups for their contri- butions in preparing the document.

Feedwater Quality Task Group

James O. Robinson, Chairman

Russ Lane

Arthur W. Fynsk, Chairman

Roger Light

Selden K. Adkins

Roger Long

Jesse S. Beecher

G.

Novitski

Wayne Bernahl

Larry Rosenzweig

Debbie Bloom

J.

J. Schuck

Joe Cameron

David E. Simon

D.

J. Connolly

John W. Siegmund

Irv J. Cotton Doug Dewitt-Dick

Patrick Thomasson Peter L. Tremont

Sam Dilcer

T.

J. Tvedt, Jr.

Robert A. Hart

R.

H. Weick

C. R. Hoefs

Alan Whitehead

Bob Holloway

J.

F. Wilkes

Industrial Subcommittee

James O. Robinson, Chairman

R.

W. Lane

Anton Banweg

P.

J. Latham

T. Beardwood

Jesse S. Beecher

Roger V. Long

D.

E. Noll

James C. Bellows, Ph.D.

Thomas H. Pike

Wayne E. Bernahl

F.

J. Pocock

Deborah M. Bloom

L.

Rosenzweig

Irvin J. Cotton

J.

K. Rice

Robert J. Cunningham

J.

J. Schuck

David Daniels

John W. Siegmund

Douglas B. DeWitt-Dick

David E. Simon II

S.

B. Dilcer, Jr.

P.

M. Thomasson

Arthur W. Fynsk

T.

J. Tvedt, Jr.

F.

Gabrielli

John R. Webb

S.

Goodstine

W.

Willsey

Karl W. Herman

J. F. Wilkes

Robert T. Holloway

David K. Woodman

K. Kelley

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CONTENTS

1

Introduction

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2

Steam Purity

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3 Problems Caused by Poor Steam Purity

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4 Causes of Poor Steam Purity

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5 Methods of Detecting Steam Purity Problems

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6 Investing a Steam Purity Problem

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7 Correcting a Steam Purity Problem

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8 Operating Guidelines to Avoid Steam Purity Problems

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9 Steam Sampling and Analysis

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Tables

1

U.S. Customary/SI Conversion Factors

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2

Code Of Federal Regulations April 1, 1993

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Figure

1

Maximum Boiler Water Silica Allowable

to Maintain <0.02 ppm Silica in the Steam

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References

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SECTION 1

INTRODUCTION

Steam purity problems have caused operating difficulties in industrial plants for decades. Some of the problems attributed to inadequate steam purity are superheater overheating; control valve sticking; turbine deposi- tion; erosion and corrosion; expansion joint and steam line cracking; product, catalyst, and humidified air contamination; and condensate sys- tem corrosion. This document was prepared to assist industrial plant operating per- sonnel in avoiding steam purity related problems, and it includes the fol- lowing descriptive sections:

• Steam Purity

• Problems Caused by Poor Steam Purity

• Causes of Poor Steam Purity

• Methods of Detecting Steam Purity Problems

• Investigating a Steam Purity Problem

• Correcting a Steam Purity Problem

• Operating Guidelines to Avoid Steam Purity Problems

• Steam Sampling and Analysis

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SECTION 2

STEAM PURITY

Steam purity is an expression of the quantity of non-water components contained in the steam. These components can be dissolved in the steam, dissolved in water droplets entrained in the steam, or carried as discrete solid particles with the steam. In total, they are the steam contamination. Steam impurities are usually expressed as the quantity in parts per million (ppm) or parts per billion (ppb) of solids contamination present in the steam. The gaseous and vaporous contaminants (CO 2 , NH 3 , SiO 2 , etc.) are not normally included in this expression of steam purity and, therefore, when they are of interest, must be measured and reported separately. A term often confused with steam purity is steam quality. Steam qual- ity relates to the quantity of moisture present in the steam — 100% qual- ity specifying no moisture content, 0% quality specifying all liquid. The concept of steam quality is important because the liquid droplets en- trained when the steam leaves the boiler contain dissolved solids. These dissolved solids represent potentially harmful steam contamination. The moisture by itself may also be harmful. If the moisture is thrown at great force against inlet stages of a turbine, it can cause damaging impingement or erosion of the turbine inlet nozzles and blades.

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SECTION 3

PROBLEMS CAUSED BY POOR STEAM PURITY

Steam purity is an important consideration in the design and operation of an industrial steam generator. The steam being generated must meet certain purity criteria to avoid adverse effects in superheaters, turbines, heaters, industrial processes and products, and condensers. The presence of excessive solid, liquid, or vaporous contamination in saturated steam can foul, damage, and ultimately cause failure of superheaters and tur- bines. The resulting efficiency losses and unscheduled outages can be very costly not only because of the repair expenses but also because of production losses and purchased power costs. The steam purity required depends on how the steam will be used. Usually, the most stringent steam purity requirements are encountered where superheated steam is used to drive a condensing turbine, or where steam contacts a catalyst that is sensitive to low level contamination. When the steam comes in direct contact with the product or process in processing and manufacturing operations, additional priority criteria may apply. If the steam is used in food processing or in the manufacture of products in contact with food, it is necessary to comply with the Federal Food and Drug Administration (FDA) and/or the U.S. Drug Administration (USDA) regulatory limitations. When steam is used for humidification, air quality requirements must be met.

3.1 Superheaters

Superheater deposits are usually caused by the entrainment of boiler water in the steam. A portion of the entrained boiler water adheres to the superheater tube surface and leaves solid deposits when the water is evaporated. This buildup of deposits may coat the internal surfaces of the superheater elements or wash down to the lower bends during shutdown. If sufficient deposit accumulates in the tube, metal temperature will in- crease to the creep range, forming blisters and often leading to tube fail- ure. Deposits sometimes accumulate enough to restrict the steam flow and cause downstream failures.

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Carryover can also cause corrosion of the superheater. Attack may vary from gouging to stress corrosion cracking. Gouging attack usually occurs at the lower bends since soluble alkaline contaminants that wash there during shutdown concentrate when condensate is boiled off during startup. Because oxygen corrosion during shutdown causes pitting of the lower bends, care must be taken to avoid confusing the two types of cor- rosion. Caustic embrittlement occurs from caustic contamination of the steam, and both halides and caustic have been known to cause stress corrosion cracking in austenitic stainless steel superheater tubes. The level of steam purity required to protect superheaters from damage varies with the superheater design and boiler operation. While individual plant operating experience must dictate system requirements, a steam solids level of less than 0.3 ppm (less than 0.1 ppm sodium) is satisfactory for most industrial boiler superheaters.

3.2 Steam Turbines

The specific level of steam purity required to avoid problems depends on the design and operation of the turbine. Both saturated and super- heated steam are used to drive turbines in industrial plants. The steam usually is in the 200 psig to 1500 psig pressure range and the superheated steam temperatures normally range from 490 o F to 950 o F. The turbines usually power an electrical generator, a mechanical drive, a compressor, a blower, or a pump; they may operate as topping, extraction-condensing or full- condensing machines.

3.2.1 Saturated Steam Turbines.

The steam purity requirements for saturated steam turbines are not stringent. Since saturated steam begins to condense in the first stage of the turbine, water soluble contaminants carried with the steam do not form deposits. Therefore, unless the steam is contaminated with solid particles or acid gases, the purity of the steam does not significantly affect the per- formance of the turbine. There may, however, be some problem with ero- sion from the abrasion of high speed droplets of condensate.

3.2.2 Superheated Steam Turbines.

Steam purity is very critical to the performance of the turbine when the turbine is driven by superheated steam. Many salts are soluble in super-

heated steam. When superheated steam is cooled as it expands through the turbine, the steam contaminants may condense, or precipitate, and adhere to the otherwise dry areas of the turbine. Deposition from steam can cause non-return valves, stop valves, control

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valves, and governor valves on turbines to stick. The potential danger of overspeed and resulting failure is a real concern. Deposits on the blades can lead to reduced efficiency and turbine imbalance. Steam contamination can also cause corrosion. As the contaminants pass through the turbine, a concentrated solution that is corrosive may form on the system metal. Localized pitting and cracking of the disks and blades can occur. Solid particles and liquid droplets in steam can cause erosion damage. Salt deposits often cause severe pitting corrosion during out-of-service periods when oxygen and moisture are both present. Operating experience suggests that the maximum acceptable level of steam contamination for most continuously operating industrial turbines is 60 ppb total dissolved solids, including 20 ppb sodium plus potassium as Na and 20 ppb silica as SiO 2 . For those systems without appreciable sodium hydroxide or sodium carbonate in the boiler water, a degassed cation conductivity of less than 1 micromho per centimeter is usually an

indication of acceptable steam purity. However, several factors should be considered when stipulating the steam purity criteria for a specific tur- bine, which include

• the steam conditions at the turbine inlet and exhaust

• the previous operating history of the turbine

• the anticipated operating conditions of the turbine

• the turbine manufacturer's specifications

Maintaining satisfactory steam purity requires continuous representa- tive sampling of saturated steam, and, perhaps superheated steam if water less pure than the saturated steam is used for direct spray desuperheating or attemperation. The steam purity should be monitored by continuous

measurement of degassed cation conductivity and/or sodium. Silica con- centrations are rarely monitored continuously, but may be checked rou- tinely by manual analysis of grab samples of steam.

3.3 Steam Line and Expansion Joints

Contamination of the steam by boiler water carryover or the attemper- ating water can cause failures. Caustic contamination in an otherwise pure steam is especially dangerous, in that it can lead to stress corrosion cracking of expansion joints and steam lines. While not a common oc- currence, catastrophic failures have occurred. Whenever high levels of carryover are encountered, affected portions of the steam lines should be washed with high-purity, amine-treated, oxygen-free water until the con- tamination is removed.

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3.4 Manufacturing Processes

Steam is widely used in industrial manufacturing processes for heating, evaporating, reforming, reacting, distilling, etc. Where steam is used di- rectly in the process, impurities can lead to catalyst fouling, fiber staining, and product contamination. Where steam is used for indirect heating, the major concern is the con- centration of corrosive gases in the condensed steam. Oxygen, carbon dioxide, ammonia, and sulfur dioxide are the most common corrodents and must be kept at low levels, or neutralized, to avoid corrosion and equipment failure. These gases and other non-condensable ones can also greatly reduce heat transfer. Because steam is used in such a wide variety of manufacturing processes, the steam purity requirements for these processes vary over a broad range. In general, the steam purity required for use in turbine drives is more than acceptable for manufacturing processes. There are notable exceptions, however, including operations in which steam is used directly in a process, e.g., catalytic processes, hospital sterilizers, pharmaceutical manufacturing, and food processing. In many cases there is a limitation on specific contaminants rather than the total level of contaminant. The steam purity criteria for each process must be established individually.

3.5 Food and Drug Processing

Where the steam has direct contact with food or food packaging ma- terials, steam contaminants can impart an undesirable taste, odor, or color. If the steam contaminant levels are outside the permitted values of the regulatory government agency, the food or drug product may be con- demned, forcing disposal rather than sale of this product. The FDA and USDA regulate the types and amounts of boiler water ad- ditives used in the preparation of steam that will contact food or food

packaging materials. The FDA lists 35 non-volatile substances and 6 volatile substances (neutralizing amines) in CFR TITLE 21, Food and Drugs, Chapter 1, Subpart D, Paragraph 173.310 (Table 1). Most non- volatile substances do not have specific limits — they are accepted on the basis that they not be used in excess of "that level required for their func- tional purpose." The six volatile substances listed by the FDA

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• cyclohexylamine

• diethylaminoethanol (DEAE)

• hydrazine

• morpholine

• octadecylamine

• trisodium nitrilotriacetate

have specific limits on the concentration allowable in steam used for food preparation. The use of these six substances is prohibited where the steam comes in contact with milk or milk products. Their use is also prohibited where the steam contacts drug components, in process materials, and in the manufacture of drugs, drug products, and drug contact surfaces. (Federal Register, June 1, 1976, Section 212.227).

3.6 Humidification

The improper use of neutralizing amine treatments in steam systems can lead to adverse health effects where steam is used for direct injection to a humidification system. Instances of skin irritation, dizziness, and lacrymation due to overfeed have been reported. The potential long-term effects of amine exposure are being scruti- nized. A recent detailed study of health risks associated with the use of morpholine and DEAE for the Department of the Navy notes uncertainties and gaps in data that make it difficult to assess the long-term effects of their usage. The report recommends continued research. [1,2] The permissible airborne exposure limits established by OSHA are 20 ppm (by volume) for morpholine, 10 ppm for DEAE, and 1.0 ppm for hy- drazine. These limits are applicable only to the workplace, with maxi- mum exposure of 8 hours a day, 5 days a week. The American Conference of Governmental Hygienists (ACGIH) has set a Threshold Limit Value- Time Weighted Average (TLV-TWA) of 20 ppm (by volume) for morpho- line and 10 ppm for DEAE, 10 ppm for cyclohexylamine, and 0.1 ppm for hydrazine. Sylvia Edgerton, et. al. of Battelle (Columbus) conducted a 30- hour study in an indoor office/laboratory steam humidified by a system in which cyclohexylamine and DEAE were added for corrosion control. The concentration in the air of each amine was less than 1 ppb. [3] Amine use in systems in which steam is used in humidification should be approached with caution. The treatment control must be fully reliable to avoid overfeed. The best method is to feed in proportion to system flow. Do not slug feed these materials at any time. Because of the obvious short-term effects of overfeed and the uncertain long-term effects, the best approach is to use a separate system to generate steam for humidification in order not to introduce into the air the amine used for condensate sys- tem protection.

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SECTION 4

CAUSES OF POOR STEAM PURITY

Poor saturated steam purity is caused by entrainment of boiler water in the steam, or by the volatilization of materials that form vapors at boiler water conditions. Poor superheated steam purity is caused either by poor saturated steam purity or direct spray attemperation with water of inade- quate purity.

4.1 Volatilization of Boiler Water Solids

The types and quantities of boiler water solids that will vaporize are controlled by the natural laws of physical chemistry. Principal among the controlling factors are pressure and temperature, concentration in the boiler water of each contaminant, and boiler water pH. The pressure and temperature are fixed for any given operation, so the only controllable pa- rameters are boiler water pH and concentration. It may be difficult to change pH without affecting other aspects of water chemistry control. For this reason, the volatile contamination of sat- urated steam is almost always controlled by maintaining the boiler water concentration of an individual contaminant below a target value. The volatile species of greatest concern in most industrial boilers is silica. Figure 1 represents the boiler water silica concentrations that correspond to a maximum of 20 ppb SiO 2 in saturated steam at various operating pressures and pH levels. Aluminum, sulfite/sulfate, and/or chloride volatility have, on occasion, caused steam contamination problems in boilers operating over 900 psig. Ammonia contamination in particular in- creases the volatility of chlorides and sulfates.

4.2 Entrainment of Boiler Water Solids

Entrainment carryover can be caused by many factors. These factors fall into three main categories: chemical, mechanical, and operational.

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100.0 80.0 60.0 40.0 20.0 10.0 8.0 6.0 4.0 2.0 1.0 0.8 0.6 0.4 0.2
100.0
80.0
60.0
40.0
20.0
10.0
8.0
6.0
4.0
2.0
1.0
0.8
0.6
0.4
0.2
0.1
400
800
1200
1600
2000
2400
2800
3200
Boiler Water Silica, ppm
1200 1600 2000 2400 2800 3200 Boiler Water Silica, ppm Drum Pressure, psig pH 9.0 and

Drum Pressure, psig

pH 9.0 and 7.8

pH 9.0 and 7.8 pH 11.3

pH 11.3

pH 10.3

pH 12.1

Figure 1: Maximum Boiler Water Silica Allowable to Maintain <0.02 ppm Silica in the Steam

4.2.1 Chemical Factors.

The chemical factors are those species that decrease the surface tension of the boiler water and thus promote the formation of a stable foam. The mate- rials that commonly cause this effect are total dissolved solids, alkalinity, cer- tain organic compounds, and suspended particulate matter. Suggested limits

for the maximum concentrations of contaminants in industrial boiler water have been published by ASME [4] and ABMA [5]. The worst problems occur when the surface tension is decreased so that steam bubbles accumulate, raising the level in the steam drum. This foam- water mixture can carry huge amounts of boiler water out of the drum into the steam line or the superheater. However, even at a lower concentration of surface-active solids, entrainment carryover of a lesser but still undesirable amount can result from the failure of the steam bubbles to break cleanly. Another aspect of foaming is the development of level control problems. The building or breaking of a foam layer may be interpreted as a water level change by the feedwater control system. This misinterpretation of the foam level as the water level will cause the feedwater regulator to respond erro- neously, producing real changes in boiler level that can cause steam conta- mination.

4.2.2 Mechanical Factors.

The design of the steam drum and the steam/water separation devices within the steam drum affects the amount of boiler water carryover. The drum should be designed with sufficient area to permit good steam/water separa- tion in the space above the normal water level. Internal steam separation de- vices should improve steam/water separation without creating excessive pres- sure losses. Several separator designs are used by the various boiler manu- facturers. These devices must be maintained as clean as possible and kept properly fastened in the correct position. Any loosening, misalignment, or cracking of baffles or buildup of heavy deposition on the screens can cause separators to malfunction and increase the mechanical carryover dramati- cally.

4.2.3 Operational Factors.

The operational factors that can cause entrainment carryover are numer- ous. Some can be conveniently corrected by modifying operating practices while others are so much a part of industrial processing requirements that making changes is difficult. Operating the boiler above its rated steam gener- ation capacity can overload the steam-water separators. They can also be over- loaded by operating the boiler below its design pressure because lower pres- sure increases the steam velocity through the separators. Operating the boiler with high water level can also overload the separators with too much water. Boilers are operated with a high water level for several reasons. Sometimes the

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operator intentionally maintains a high water level to avoid other prob- lems. Other times the drum level instrumentation gives a false indication of the level over the full length of the steam drum, or the steam load swings are of sufficient magnitude that a loss in pressure causes a surge in drum water level.

4.3 Attemperating Water Contamination

Contaminants are often introduced into steam by water that is added to control steam temperature. Since this "attemperating" water becomes part of the steam, impurities in the water contaminate the steam. Common causes of attemperating water contamination are the feed of non-volatile treatment chemicals and the return of condensate system corrosion products. Both contaminants can lead to deposits in the steam system. Less commonly encountered, but more dangerous, is contamina- tion by demineralizer or condensate polisher regenerants. Sodium hy- droxide and sulfuric acid contamination of steam systems has cost indus- try millions of dollars in steam line and turbine replacement repair.

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SECTION 5

METHODS OF DETECTING STEAM PURITY PROBLEMS

Unfortunately, many times the first recognized symptom of a steam pu- rity problem is equipment failure. In most instances, monitoring the chemistry of steam, boiler water, and feedwater and a regular review of control room data will provide early warning before damage occurs. When steam contamination is detected, it is important to identify whether the poor steam purity is due to steam drum carryover or contaminated at- temperating water, since problem resolution follows different paths for each source of contamination.

5.1 Control Room Monitoring

Steam purity is very sensitive to steam flow, boiler contaminant level, and drum water level. Steam purity should be checked if these opera- tional parameters either exceed normal limits or start fluctuating. The fol- lowing incidents may indicate an excessive carryover situation requiring further investigation. (1) Superheated steam temperature drops. Sudden temperature drops are normally the result of large amounts of water being carried into the superheater. The heat required to evaporate the water causes a drop in steam temperature. Foaming, priming, or other more grad ual decay of performance may cause a decrease in superheated steam temperature. (2) High or fluctuating drum level. High drum level and quickly fluct uating levels are the cause of many carryover problems. Even when the drum level is steady during stable loads, load changes can pr oduce fluctuating drum levels that cause excessive carryover. (3) Header pressure variations. Variations in steam header pressure caused by changing load demands often lead to serious carryover problems. Variable header pressure often causes high and fluctua ting drum levels. (4) Loss of efficiency. Low superheater outlet temperatures, decreases in spray water usage, or increased fuel usage may indicate insulating deposits in the superheater or the requirement for additional heat to

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evaporate carryover moisture. (5) Increasing superheater tube temperatures. An increase in metal temperature as measured by thermocouples on individual supe rheater circuits may indicate a buildup of deposit inside the tubes. (6) Turbine pressure. A buildup of first stage turbine pressure is often a sign of turbine fouling. By maintaining a record of turbine stage pressure vs. steam flow under similar operating conditions, turbine fouling can be detected. (7) Loss in turbine generator or compressor capacity. As a turbine becomes fouled with deposition, the maximum output from the dr ven machine is reduced. (8) Sticking steam admission, regulator and stop valves. The buildup of deposits on valve stems can cause malfunctions and are usually a sign of steam contamination.

5.2 Chemical Monitoring

Steam purity is very sensitive to any level of chemical contamination throughout the boiler feedwater system. While a direct measurement of steam purity is the most precise method of identifying steam purity prob- lems, the monitoring of other streams can provide an indication of po- tential difficulties. (1) Steam Purity Monitoring. Steam samples should be collected using nozzles and sampling procedures in accordance with ASTM D-1066, ASME PTC 19.11, or EPRI TR-100196, where high steam purity is dictated by turbines that operate with superheated inlet steam, by boilers with su- perheaters, or by strict process requirements. (See Section 9, Steam Sampling and Analysis.) When proper sampling nozzles are not available, samples collected through pipe nipples can often be used to detect trends and identify fac- tors that affect carryover. However, every effort should be made to install proper sampling nozzles to ensure an accurate evaluation. Since foam-expanded boiler water rides above the water level that is indicated by gauge glasses and most instrumentation, the installation of sampling probes before the final dryers will sometimes enable detection of foaming. The most common design for these probes is a perforated pipe collector located about 6 in. to 12 in. above normal high water level and before the final dryers. Conductivity measurements of condensate from these probes are normally adequate to detect the difference between steam, foam over, and boiler water. (2) Attemperation and Desuperheating Water Monitoring. Water used for steam attemperation or desuperheating should be monitored on a con-

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tinuous basis. The type of monitoring required will depend on the ulti- mate steam purity requirements; however, sodium analysis and/or de- gassed cation conductivity measurement will usually prove satisfactory. (3) Boiler Water Monitoring. Boiler water contamination can often lead to steam purity problems. The boiler water conductivity should be moni- tored on a regular basis and consistently maintained within a specified control range that has been determined suitable for the plant. The pres- ence of contamination as a result of ion exchange regenerant introduction or condensate contamination should be detected and action taken to con- trol boiler water chemical contaminant levels within a defined range at all times.

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SECTION 6

INVESTIGATING A STEAM PURITY PROBLEM

In order to correct a steam purity problem, its cause must be identified.

The first step is to determine the source of steam contamination. Does the contamination come from steam drum carryover, attemperator spray water, or exfoliation of the system metal? If steam purity is monitored, a test program can determine the source of contamination. The cause of a steam purity problem — drum internals failure, foaming, priming, surg- ing, high loads, high drum levels, contamination of attemperating water, or exfoliation of superheater metal — must be determined by an overall assessment of plant operating data.

6.1 Review of Plant Records

A careful review of a unit's chemistry logs and control room charts is

often sufficient to identify the causes of steam contamination. Drum water level, steam flow, feedwater flow, drum pressure, and the amount of spray

water used are important parameters to check. Steam temperature and su- perheater metal temperatures may indicate massive carryover situations, especially if the situation occurs quickly. Saturated steam, spray water, and boiler water analyses for sodium, al- kalinity, TDS, specific and cation conductivity should be reviewed. The specific conductivity of saturated steam and condensate are sufficient to detect massive carryover incidents.

6.2 Deposit Analyses

Identification of deposit constituents helps establish the source of steam contamination. Iron and copper oxide deposits present in the industrial steam system usually result from corrosion products in the attemperating water or exfoliation of iron oxide from superheater or other steam system components. The sodium salts of sulfate, chloride, and phosphate are usu ally the result of boiler water entrainment in the steam, although they

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could also be present from attemperating water contamination. Silica de- posits may be the result of either boiler water entrainment in the steam or selective vaporization of silica from the boiler water. Sodium hydroxide deposits may be present as the result of either boiler water entrainment in the steam or demineralizer regenerant contamination of the attemperat- ing water. Acidic sulfur deposits may result from the decomposition of sodium sulfite in boilers operating above 900 psig, contamination of at- temperating water, or acidic sulfur gases being returned with the conden- sate. Other deposits such as aluminum, titanium, and barium need to be traced for their source of entry into the system.

6.3 Steam Drum Inspection

The steam drum and its internals should be inspected whenever a unit is brought down for inspection. This physical inspection can sometimes

identify specific causes of steam purity problems. Items to check are listed below.

• loss of mechanical integrity in the drum internals, especially in those areas that allow entrance of boiler water into the steam flow

• gaps or missing plugs that might result in short circuiting of the steam–water mixture, bypassing drum internals or dryers

• pluggage of dryer screen plates

• indication of high water level

• variable or uneven water level

• improper feedwater distribution causing turbulence

• condition and location of chemical feed, feedwater, and continuous blowdown lines

6.4 Drum Level Measurement

Drum level control instruments are often calibrated by the gauge glasses. At the operating pressures found in most units generating steam for turbines, there can be a sub-cooling error in the gauge glass reading. The drum level control calibration needs to be properly adjusted for this sub-cooling error.

6.5 Steam Purity Studies

A test program that varies chemical and operational parameters may be required to identify the cause of a steam purity problem and to define con- ditions under which the steam generator will produce acceptable steam purity. Effective monitoring requires simultaneous steam, boiler water, and

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feedwater sampling while control room data is recorded. Steam samples should be flowing for at least 24 hours before the test, and the sampling rate should be in accordance with the ASTM specification for isokinetic sampling. All samples should flow continuously throughout the test pe- riod. A typical test procedure for determining boiler steam purity perfor- mance under base load conditions is described below. Several hours before the test, boiler water dissolved solids should be established at the level normally maintained by the plant by adjusting the continuous blowdown valve setting if necessary. Steam samples should be collected through properly designed sampling nozzles and coolers and fed to the bottom of an overflowing plastic bottle or to an on-line an- alyzer. Drum water level should be established about 3 in. to 4 in. below normal but definitely above the low water level cutoff. If possible, the steam flow at the start of the test should be established at 50% of the de- sign capacity. When the boiler has been stable for 15 minutes, collect a saturated steam sample, a boiler water sample, and a feedwater sample. Record time, date, steam flow, feedwater flow, drum water level, spray water flow, drum pressure, load, and gauge glass water level. When the above steps have been completed, increase the steam flow to 75% of rated capacity and repeat the initial steps, then increase the steam flow to 100% of rated capacity. By adjusting drum water level, blowdown, and chemical additives such as antifoam chemicals, an over- all picture of the boiler steam purity performance under base load condi- tions can be developed. Variations in boiler load, drum level, and header pressure frequently cause a deterioration in steam purity not found at base load conditions. Because many steam purity problems are caused by operating transients, continuous monitoring of steam purity during normal operation is often required to identify the operating conditions that cause steam purity prob- lems.

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SECTION 7

CORRECTING A STEAM PURITY PROBLEM

To correct a steam purity problem, a careful investigation must first be conducted to determine its cause. Once the cause has been determined, corrective action can be initiated.

7.1 Attemperating and Desuperheating Water

The use of contaminated attemperating or desuperheating water must be avoided. Protection against steam contamination by this water can best be provided during system design. For example, contamination from ex- ternal sources can be reduced by using a "sweet water" condenser, which controls steam temperatures with condensed steam injection. If the con- denser is cooled with high purity water, small leaks in the condenser will not cause serious contamination. When attemperating water from other sources is used, contamination by solids-forming treatment chemicals, oxygen, and ion exchange system regenerants must be avoided. The water source should also be protected from contamination by system corrosion products.

7.2 Mechanical Carryover

Mechanical carryover is often caused by the separation equipment in the steam drum not working to specification. The causes of this are dis- cussed in section 4.2.2. The problems can often be mitigated by operat- ing at a lower-than-design yet safe water level, or by reducing the steam generation rate until permanent repairs or design changes can be made. Keeping the drum level constant or within a narrow band is crucial for producing clean steam. Base loading individual boilers prone to variable load carryover, or requiring that plant steam demand be regulated to avoid sharp increases in steam requirements, can reduce these problems. When changes in steam demand cannot be reduced to a level that the boilers are capable of meeting safely, the installation of steam accumula-

23

tors may be necessary.

7.3 Chemical Carryover

Chemically induced carryover is caused by impurities in the boiler water. The best action is to remove the contaminants from the feedwater by improving the purity of the make-up and condensate streams and in- creasing the quality and quantity of condensate returned. Another possi- ble action is to reduce the impurities at some loss of efficiency, by in- creasing blowdown. The increased blowdown will decrease the cycles of concentration and consequently the level of impurities in the boiler. The level of carryover may be mitigated by the proper feed of an "an- tifoam" chemical, which modifies the surface tension of the boiler water. These compounds, usually polyhydric alcohols, are not panaceas and should not be used as a substitute for correcting the root cause of the car- ryover problem. Their application should be tried cautiously with careful steam purity measurements to monitor the effect. If beneficial, antifoam chemical feed can sometimes be used to counteract the effects of un- avoidable operational problems, such as excessive or rapidly fluctuating steam generation load.

7.4 Off-Line Improvements

When a unit has been brought down to correct a steam purity prob- lem, it must be inspected. It is critical this be done before any water wash- ing or other cleanup. The most visible indication of a steam purity prob-

lem is salt deposits. A water wash will dissolve these deposits, leaving lit- tle trace of the problem. When the unit is inspected, several items should be examined:

1. Are the drum internals intact? If not, or if some are damaged or fouled, the carryover was caused by poor steam/water separation. The corrective measures are obvious — tighten or plug, realign, and clean the existing de- vices.

2. Is the water line in the steam drum at a constant and proper ele- vation? High water level may cause steam contamination because it has reduced the steam release space. Proper adjustment of the drum level controller is required to consistently maintain the proper drum level.

3. Is the water line in the steam drum at a consistent level through out the length of the drum? Uneven heat distribution or insufficient steam release area may produce

24

a "swelling" of the boiler water in one area of the drum, which

causes carryover. Firing patterns should be checked and adjusted

if necessary.

4. Is the feedwater line intact, all openings clear and pointed in the proper direction?

Improper feedwater distribution may cause spray in the steam space and overloading of the steam separators.

5. Is the continuous blowdown line intact and properly located?

If not, samples can give a misleading indication of boiler water

concentrations. It may also be possible to improve steam purity by adding new sepa- rators or revising the existing design, but such changes should be ap- proached very cautiously with before-and-after testing to ensure that the change is beneficial. External separators are a possible solution if additional mechanical separation is needed that cannot be accommodated in the steam drum. A major disadvantage of an external separator is that the piping between the steam drum and the separator is especially susceptible to erosion and cor- rosion because of the entrained water droplets.

7.5 After Correcting the Problem

After steam contamination has occurred and corrective action taken, it is recommended that contaminated superheaters and steam lines be flushed for a sufficient time with the highest purity water available to re- move residual deposition. Otherwise, the residual deposition may lead to additional operating problems. This water should be treated with a volatile alkalizing agent, such as ammonia or a neutralizing amine, to in- crease the pH to 9.0 or greater. If oxygen is present, a volatile oxygen scavenger should also be added. If the equipment is out of service for an extended period of time, it should be protected from corrosion by fol- lowing the proper lay-up procedures.

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26

SECTION 8

OPERATING GUIDELINES TO AVOID STEAM PURITY PROBLEMS

The basic principles of producing clean steam consistently are pro- vided below. (1) Operate the boiler only at or below its rated capacity. If steam production exceeds the design rating, the separation equipment in the steam drum may not perform to specification. (2) Keep the drum level constant. Tune the drum level controls properly for the load to be run; a boiler running at half capacity will require different tuning than one running at full load. (3) Monitor the boiler blowdown routinely. This will ensure that the proper amount of water is being blown down and boiler solids are not excessive. The tests that need to be run depend on boiler chemistry. Common tests are for silica, alkalinity, conductivity, and boiler internal treatment residuals. (4) Sample the steam routinely and check for carryover. This requires isokinetic sample nozzles and sample coolers to fully condense the steam and cool it to ambient temperature. The steam should be tested for sodium or degassed conductivity and silica. (See Section 9, Steam Sampling and Analysis.) (5) Monitor attemperating water for sodium or degassed cation conductivity. These items are not all inclusive; however, careful attention to them will minimize the possibility of steam contamination and its associated problems.

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SECTION 9

STEAM SAMPLING AND ANALYSIS

It is imperative that steam samples be as representative of the steam as possible in order to determine the quantity of impurities contained in the steam. Upon proper collection of a representative sample, an accurate measurement of the impurities contained in the steam can provide infor- mation that can be utilized to determine whether or not the steam purity is within the required range to preclude damage or deterioration of such downstream equipment as superheaters, turbines, dryers, etc. These im- purities may be solids, liquids, or gases.

9.1 Steam Sampling

Steam should be sampled in accordance with the procedures de- scribed by ASTM D-1066, ASME PTC 19.11, or EPRI TR-100196. All of these procedures describe nozzles designed to collect a representative sample of steam from a saturated steam line containing liquid droplets. The placement of the nozzles and the sample flow rates as described in these procedures are essential parts of representative sampling. Procedures for sampling superheated steam are also described by ASTM D-1066-82 and ASME PTC 19.11. Superheated steam is difficult to sample reliably because contaminants that vaporize in the superheated steam will deposit on the surface of the sample line unless the sample is properly conditioned. To avoid deposition on the sample line wall, a por- tion of the condensed, cooled sample should be injected into the sam- pling nozzle to remove all of the superheat from the steam sample as it is removed from the system. Because superheated steam is difficult to sam- ple reliably, saturated steam sampling is preferred in most instances. Whether saturated or superheated steam is being sampled, the sample should be allowed to flow for a period of 24 hours prior to collection for analytical work to ensure that the nozzle and all associated piping are clean.

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9.2 Analyses

Analytical procedures may be found in the ASTM Power Plant Water Analysis Manual and numerous other analytical documents.

Sodium Ion

As a general rule, sodium ion in the steam from an industrial steam gener- ator is considered to represent one-third of the total dissolved solids. It, there- fore, provides a good means of monitoring steam purity. The sample can be continuously analyzed by means of a sodium-specific ion electrode, or grab samples can be analyzed by the same method or by flame photometry, atomic absorption, ion chromatography, or inductively coupled plasma. The choice of analytical method depends on the sodium concentration of interest, the loca- tion of the test, and the duration of the testing. The specific ion electrode is the most suitable for continuous measurement in most plant environments.

Silica

If the maximum allowable silica limits in the bulk boiler water are ex- ceeded, excessive amounts of silica will volatilize and be carried over in the steam as silicic acid. Where the steam is being utilized to drive rotary equip- ment, the silica can deposit on the blading as the pressure and temperature are reduced. Silica in the steam can be monitored either on a continuous basis or on a grab sample. In either case, the analysis is performed utilizing photometric methods of either heteropoly blue or molybdosilicate. To avoid phosphate ion interference, oxalic acid is added to the sample.

Specific Conductivity

Specific conductivity is an indirect method of determining the total dis- solved solids. It is a measure of the ability of an aqueous solution to conduct an electrical current — the greater the amount of dissolved solids in solution, the more electrical current the solution can conduct. Specific conductivity is an excellent monitor for the detection of high level steam contamination. When lower level contaminant detection is required, the specific conductiv- ity should be measured on a degassed sample since dissolved gases, i.e., am- monia, volatile amines and carbon dioxide, have a great influence on con- ductivity. To increase the sensitivity of anionic contaminant detection, de- gassed cation conductivity is recommended; however, it should be noted that cation conductivity will not detect sodium hydroxide.

Chloride Ion

The chloride ion has been shown to contribute to the deterioration of turbine blading. It can be monitored either on a continuous basis or on grab samples. Analysis can be performed either by chloride specific ion- electrode or ion chromatography.

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Metal Oxides

Since metal oxide particles may contribute to turbine blade damage and may indicate superheater tube deterioration, their measurement is in- cluded in this section. The analytical work is performed on a grab sample and run either by atomic absorption or inductively coupled plasma. Low level colorimetric tests are also available. For gross suspended metallic oxides, 0 micron to 0.45 micron filters can be utilized and compared to standard charts for an estimation of the oxide content of the steam.

9.3 Deposit Analysis

Steam system deposits should be analyzed for their composition to aid in the identification of their cause. Analysis by x-ray diffraction and fluo- rescence are common. Other techniques used to identify specific condi- tions include scanning electron microscopy, energy dispersive spec- troscopy, Fourier transform infra-red spectroscopy, and gas chromatogra- phy (mass spectrometry and ion chromatography).

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32

TABLES

33

34

TABLE 1

U.S. CUSTOMARY/SI CONVERSION FACTORS

U.S. Customary

 

SI

1 gallon

 

3.78

liters

1 inch

 

2.54

centimeters

1 micromho

1

microsiemens

212 o Fahrenheit

 

100 o Celsius

1 part per million (ppm)

1

milligram per liter

1 psig

 

7.03

kilo pascal

1 part per billion (ppb)

1

microgram per liter

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TABLE 2

CODE OF FEDERAL REGULATIONS April 1, 1993

Subpart D — Specific Usage Additives

§ 173.310 Boiler Water Additives

Boiler water additives may be safely used in the preparation of steam that will contact food, under the following conditions:

(a)

The amount of additive is not in excess of that required for its func- tional purpose, and the amount of steam in contact with food does not exceed that required to produce the intended effect in or on the food.

(b)

The compounds are prepared from substances identified in para- graphs (c) and (d) of this section and are subject to the limitations, if any described.

(c)

List of substances:

Substances

Acrylamide sodium acrylate resin

Acrylic acid/2-acrylamide-2-methy propane sulfonic acid co-polymer having a mini- um weight average molecular weight of 9,000 and a minimum number average molecular weight of 5,700 as determined by a method entitled "Determination of Weight Average and Number Average Molecular Weight of 60/40 AA/AMPS" (October 23, 1987), which is incorporated by reference in accordance with 5 U.S.C. 552(a). Copies may be obtained from the Division of Food and Color Additives, Center for Food Safety and Applied Nutrition (HFF-330), Food and Drug Administration, 200 C St. SW, Washington, DC 20204, or may be exam- ined at the Office of the Federal Register, 1100 L St. NW, Washington, DC. Ammonia alginate Cobalt sulfate (as catalyst 1-hydroxyethyidene-1, 1-diphosphonic acid (CAS Reg. No. 2809-21-4) and its sodium and potassium salts

Limitations

Contains not more than 0.05 percent by weight of acrylamide monomer.

Total not to exceed 20 parts per million (ac- tive) in boiler feedwater.

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Substances

Lignosulfonic acid

Limitations

Total not to exceed 20 parts per million (ac- tive) in boiler feedwater.

Monobutyl ethers of polyethylene-poly- propylene glycol produced by random condensation of a 1:1 mixture by weight of ethylene oxide and propylene oxide with butanol Poly (acrylic acid-co-hypophosphite), sodium salt (CAS Reg. No. 71050-62-9), produced from a 4:1 to a 16:1 mixture by weight of acrylic acid and sodium hy- pophosphate

Polyethylene glycol Polymaleic acid (CAS Reg. No. 26099-09-2), and/or its sodium salt (CAS Reg. No.

30915-61-8)

Polyoxypropylene glycol Potassium carbonate Potassium tripolyphosphate Sodium acetate Sodium alginate Sodium aluminate Sodium carbonate Sodium carboxy-methylcellulose

Sodium glucoheptonate Sodium hexametaphosphate

Minimum molecular weight 1,500

Total not to exceed 1.5 parts per million in boiler feedwater. Co-polymer contains not more than 0.5 percent by weight of acrylic acid monomer (dry weight basis).

As defined in § 172.820 of this chapter

Total not to exceed 1 part per million

boiler feedwater (calculated as the acid)

in

Minimum molecular weight 1,000

Contains not less than 95 percent sodium carboxymethylcellulose on a dry-weight basis, with maximum substitution of 0.9 carboxymethylcellulose groups per anhydroglucose unit, and with a min- imum of viscosity of 15 centipoises for 2 percent by weight aqueous solution at 25 o C; by method prescribed in the “Food Chemicals Codex”, 3rd Ed. (1981), pp. 280–282, which is incorporated by ref- erence. Copies may be obtained from the National Academy Press, 2101 Constitution Avenue, NW, Washington, D C 20418, or may be examined at the Office of the Federal Register, 1100 L St. NW, Washington, DC 20408.

Less than 1 part per million cyanide in the sodium glucoheptonate.

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Substances

Sodium humate Sodium hydroxide Sodium lignosulfonate Sodium metabisulfite Sodium metasilicate Sodium nitrate Sodium phosphate (mono-, di, tri) Sodium polyacrylate Sodium polymethacrylate Sodium silicate Sodium sulfate Sodium sulfite (neutral or alkaline) Sodium tripolyphosphate Tannin (including quebracho extract) Tetrasodium EDTA Tetrasodium pyrophosphate

Limitations

Less than 1 part per million cyanide in the sodium glucoheptonate.

(d) Substances used alone or in combination with substances in para- graph (c) of this section:

Substances

Limitations

Cyclohexylamine

Not to exceed 10 parts per million in steam, and excluding use of such steam in con- tact with milk and milk products

Diethylaminoethanol

Not to exceed 15 parts per million in steam,

Hydrazine

and excluding use of such steam in con- tact with milk and milk products Zero in steam

Morpholine

Not to exceed 10 parts per million in steam,

Octadecylamine

and excluding use of such steam in con- tact with milk and milk products Not to exceed 3 parts per million in steam,

Trisodium nitrilotriacetate

and excluding use of such steam in con- tact with milk and milk products Not to exceed 5 parts per million in steam, and excluding use of such steam in con- tact with milk and milk products

(e) To assure safe use of the additive, in addition to the other informa- tion required by the Act, the label or labeling shall bear:

1. The common or chemical name or names of the additive or ad- ditives. 2. Adequate directions for use to assure compliance with all the provisions of this section.

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REFERENCES

1. "An Assessment of the Health Risks of Morpholine and Diethylaminoethanol" by the Committee on Toxicology, National Research Council, National Academy Press, Washington, D.C., August, 1983.

2. Wilkes, J. F., Commercial – Industrial Water and Steam Treatment — Effect on Humidification. ASHRAE Publication No. 72-12, pp.

16–23.

3. Edgerton, S. A., D. U. Kenny, and D. W. Joseph. "Determination of Amines in Indoor Air From Steam Humidification." Environmental Science & Technology, 23:4, 1989.

4. American Society of Mechanical Engineers, Consensus on Operating Practices for the Control of Feedwater and Boiler Water Quality in Modern Industrial Boilers, 1994.

5. American Boiler Manufacturers Association, Boiler Water Limits and Steam Purity Recommendations for Watertube Boilers, 3rd Edition, 1983.

6. Jonas, O., "Development of a Steam Sampling System," EPRI TR- 100196 Research Project 2712-8, December, 1991.

7. Robinson, J. O., A. W. Fynsk. "A Practical Guide to Avoiding Steam Purity Problems in the Industrial Plant." International Water Conference, October 1992.

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