Chemical Cleaning of Water Systems
Chemical Cleaning of Water Systems
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An Introduction to Chemical Cleaning of Industrial Water Systems – H03-003
This course was adapted from the Unified Facilities Criteria of the
United States government, which is in the public domain.
An Introduction to Chemical Cleaning of Industrial Water Systems – H03-003
CONTENTS
1. GENERAL GUIDANCE
2. REMEDIAL CLEANING PROCEDURES
3. DEVELOPING A WATER TREATMENT PROGRAM
4. REPORTS AND AUDITS
5. GLOSSARY
1. GENERAL GUIDANCE. Chemical cleaning of water systems can be divided into two
classifications: pre-operational and remedial. Pre-operational cleaning is performed to
prepare the water-contacted metal surfaces to receive chemical treatment, which
provides protection from scale, corrosion, and microbiological growth. Remedial
cleaning is performed to restore water systems that have been fouled with scale,
corrosion products, and microbiological growth due to inadequate or ineffective water
treatment. Cleaning, particularly remedial-type cleaning, is often performed by outside
contractors familiar with cleaning procedures, techniques, and safety. It should be noted
that if the water system is significantly scaled, the chemical treatment program was
obviously inadequate and was not properly designed, set-up, controlled, or applied.
After cleaning has been completed, the chemical treatment program and quality control
(QC) program must be improved so the same problem does not recur. Use of a well-
designed quality assurance (QA) program would have produced identification and
notification of potential and developing problems before they became serious. Pre-
operational cleaning is often performed by contractors responsible for the fabrication of
the water system before turning it over to the owner. Water system operations
personnel must assess the effectiveness of any cleaning process that has been
performed.
The requirement for performing a pre-operational cleaning process is usually written into
the specification for new construction of a water system that must be performed by a
mechanical contractor. The mechanical contractor is required to perform the work as
directed in the specifications; however, if the specifications are not appropriate for the
specific system, including consideration of all system metallurgy, the cleaning process
may contribute to corrosion to mild steel, galvanized steel, copper, or aluminum, or it
may result in incomplete cleaning of dirty and corroded metal surfaces. The
specifications should be reviewed by a qualified base inspector or qualified independent
consultant to ensure that cleaning agents and procedures have been specified
appropriately. A contracting officer or other individual responsible for QA should inspect
the equipment after cleaning and document the effectiveness of the cleaning process.
1.2.1 SAFETY AND ENVIRONMENTAL ISSUES. Remedial cleaning may pose safety
issues for personnel handling acids, caustics, and various chemicals. There could also
be environmental concerns associated with chemical disposal. Inexperienced personnel
should not perform the chemical cleaning of an industrial water system.
1.2.2 CONTRACTING CLEANING SERVICES. For some cleaning jobs, such as large
boilers and cooling towers, it may be advisable to engage a service company
1.4 TYPES OF DEPOSITS. The deposits that occur in water systems can be inorganic
mineral salts and corrosion products or organic (oily) or biological in nature. Deposits
range in composition from very dense crystalline structures, to very porous and loosely
bound materials, to gelatinous slimes. Most of the deposits formed from water
constituents consist of corrosion products such as iron and copper oxides, mineral
scales, or mixtures of these materials.
deposits may form in cooling systems from bacterial or algae growths, or from
decomposition products of various microorganisms.
1.4.2 BOILER DEPOSITS. Boiler deposits may take various forms. In low-pressure
boilers using a relatively hard feedwater, deposits are essentially calcium and
magnesium, silicates, sulfates, carbonates, phosphates and hydroxides, plus some
organics. Deposits may also contain considerable amounts of silica, iron, and copper.
These deposits can be spongy or porous or relatively hard and glass-like. Deposits of
the latter characteristic occur where silica is present in appreciable quantities in the
boiler water. Deposits in medium-pressure to high-pressure boiler systems usually are
mixtures of iron and copper oxides and phosphates. Dense deposits may tend to form in
high-heat transfer areas. Considerable quantities of sludge-type accumulations may be
found in downcomers, mud drums, waterwall headers, crossover tubes, and areas of
low water circulation in the boiler.
2.1.1 MECHANICAL METHODS. Mechanical methods are the oldest techniques used
for removing deposits. To perform an adequate mechanical-type cleaning, the
equipment to be cleaned may need to be partially or entirely dismantled. Even when
equipment is dismantled, some areas may be extremely difficult to reach and clean.
Chemical cleaning has largely replaced mechanical process equipment cleaning as the
most satisfactory method of removing deposits; however, mechanical methods such as
wire brushing, tumbling, scraping, and abrasive blasting with sand and grit are still
employed in special applications.
2.1.2 CLEANING AGENTS. Cleaning agents may be broadly classified as being acid,
alkaline, organic, or solvent cleaners. There is no general or universal cleaner that
removes all deposits. The selection of a solvent or cleaning agent is based on the
material's ability to remove or dissolve the deposit, as well as on cost considerations,
safety hazards, and the effect of the cleaning material on the metals involved.
2.2.4 METALLIC OXIDES. Most metallic oxides found in deposits can be removed with
hydrochloric acid. The rate of dissolution is a function of temperature and solution
velocity. If copper oxides are present on steel surfaces, special precautions are needed
to prevent copper metal plate-out on the steel.
2.2.5 SILICA AND SULFATE SCALE. Heavy silica and sulfate scale is almost
impossible to remove with hydrochloric acid. Special chemicals and procedures are
required to remove this scale.
2.3 SULFAMIC ACID. Sulfamic acid is an odorless, white, crystalline solid organic acid
that is readily soluble in water. An inhibited sulfamic acid compound, in a dry powder
form, is available under Specification MIL-B-24155, Boiler Scale Removing Compound.
A 5 to 20% solution (2 to 9 kilograms to approximately 38 liters of water [5 to 20 pounds
to approximately 10 gallons of water]) is used for removing scale from metal surfaces.
The following information pertaining to sulfamic acid should be considered:
• The dry powder form of sulfamic acid is safer to handle than a liquid solution of
hydrochloric acid; however, aqueous solutions of sulfamic acid are much slower
in action and require heating to remove scale. The sulfamic acid solution is
heated to a temperature in the range of 54 to 71 °C (130 to 160 °F) to obtain the
same fast cleaning time that is achieved by using hydrochloric acid at room
temperature. Sulfamic acid is more effective on sulfate scale than hydrochloric
acid.
The necessary corrosion inhibitors can be added to the dilute acid solution.
Users of small quantities of acid cleaners (possibly less than 38 liters [10 gallons]
of diluted acid per year) may not be able to justify purchasing undiluted acid and
spending the time, cost, and effort to prepare the cleaning solution; therefore,
consider the specific requirements before ordering.
2.4 CLEANING PREPARATION. The unit to be cleaned must be isolated from other
parts of the system. For systems that cannot be isolated by the closing of valves,
isolation may be accomplished using rubber blankets, wooden bulkheads with seals,
inflatable nylon or rubber bags, rubber sponge-covered plugs, or blind flanges and steel
plates with rubber seals. Long lines may require auxiliary connections for chemical
cleaning. The following information should be considered before the cleaning process is
started:
1. Fill the boiler or system with preheated (71 to 77 °C [160 to 170 °F]) dilute
inhibited acid solution.
2. Allow the dilute inhibited acid solution to remain in place for 8 hours.
Circulate the acid solution for approximately 15 minutes each hour at a
rate of about 3.15 liters per second (50 gallons per minute) to ensure good
mixing.
3. Keep the temperature of the acid solution preheated at 71 to 77 °C (160 to
170 °F). Measure and record the temperature at least once every 30
minutes.
4. Check and record the acid strength at least every hour (see paragraph 9-
2.6).
5. Drain the system by forcing the acid solution out using 276 to 345
kilopascals (40 to 50 pounds per square inch gauge) nitrogen; follow
Federal Specification A-A-59503, Nitrogen, Technical, Class 1. If leaks
develop when the system is under nitrogen pressure, you must use an
alternate method for removing the acid, such as pumping.
6. Fill the boiler with preheated (65 to 71 °C [150 to 160 °F]) water and soak
at this temperature for 15 minutes.
7. Drain under nitrogen pressure of 276 to 345 kilopascals (40 to 50 pounds
per square inch gauge).
2.5.2 CIRCULATING METHOD WITHOUT HEAT. The steps below describe a typical
process for descaling smaller equipment, such as enclosed vessels or hot water heater
coils, without heating the inhibited acid solution:
1. Note that an acid cleaning assembly may consist of a small cart on which is
mounted a pump and an 18.9- to 189-liter (5- to 50-gallon) steel or
polyethylene tank with a bottom outlet to the pump.
2. Install sill cocks at the bottom of the water inlet of the heat exchanger and
the top of the water outlet so that a return line can be connected directly from
the acid pump and from the heat exchanger to the acid tank.
3. Prepare an inhibited acid cleaning solution.
4. Pump the acid solution into the heat exchanger through the hose
connection. Continue circulation until the reaction is complete, as
indicated by foam subsidence or acid depletion.
5. If the scale is not completely removed, check the acid strength in the
system. If the acid strength is less than 3%, add fresh acid solution and
continue circulation until the remaining scale is removed. Usually an hour
of circulation is adequate.
6. Drain the heat exchanger.
7. Neutralize remaining acid by circulating a 1% sodium carbonate (soda ash)
solution (about 3.6 kilograms per 38 liters [8 pounds per 100 gallons]) for
about 10 minutes.
8. Rinse thoroughly with water until the pH of the rinse water is pH 8 to 10.
1. Prepare an inhibited dilute acid solution (see paragraphs 9-2.2 and 9-2.3)
in a container of suitable size.
2. Depending on the item to be cleaned and the types of scale involved, you
may want to place an agitator (mixer) in the tank or install a pump outside
the tank to circulate the acid solution. A method to heat the acid may be
required, such as a steam coil. All equipment must be explosion-proof and
acid-resistant.
3. Immerse the item to be cleaned in the dilute acid solution. Continue
soaking until the reaction is complete as indicated by foam subsidence or
acid depletion.
4. If the scale is not completely removed, check the acid strength (see
paragraph 9-2.6). If it is less than 3%, add additional acid and continue
soaking the items until the remaining scale is dissolved. Usually 1 to 2
hours of soaking is adequate.
5. Remove item from tank.
2.6 CHECKING ACID SOLUTION STRENGTH. The initial strength of the dilute
inhibited acid will vary from 5 to 20%, although 10% is typical. As the acid is consumed
by dissolving the scale, the strength of the acid decreases. The strength of the acid
solution should be measured periodically during a cleaning operation. When the acid
strength falls below 3%, the solution may be discarded since most of its scale-dissolving
capability will have been used. Use the following procedure to check the acid strength:
Apparatus:
Burette, 25 milliliters (0.8 ounce) automatic (for sodium hydroxide solution)
Stirring rod
Bottle, with dropper, 50 milliliters (2 ounces) (for phenolphthalein indicator
solution)
Graduated cylinder, 10 milliliters (0.3 ounce)
Casserole, porcelain, heavy duty, 210-milliliter (7.1-ounce) capacity
Reagents:
Sodium hydroxide solution, 1.0 normality (N)
Phenolphthalein indicator solution, 0.5%
Method:
1. Measure 10 milliliters of acid solution accurately in the graduated cylinder.
4. Fill the automatic burette with the 1.0 N sodium hydroxide solution; allow
the excess to drain back into the bottle.
5. While stirring the acid solution constantly, add sodium hydroxide solution
from the burette to the casserole until color changes to a permanent faint
pink. This is the endpoint. Read the burette to the nearest 0.1 milliliter
(0.003 ounce).
Results:
1. For hydrochloric acid:
Percent hydrochloric acid = milliliter of 1.0 N sodium hydroxide x 0.36
2. For sulfamic acid:
Percent sulfamic acid = milliliter of 1.0 N sodium hydroxide x 0.97
3.1 GENERAL INFORMATION. Although each water treatment program may contain
unique aspects, the strategic goals of every program are regulatory compliance and
safety, protection of water-contacted equipment, and acceptable costs. Achieving these
goals requires the cooperative efforts of personnel from several areas, including
environmental protection, engineering, contracting, operations, and outside resources.
Outside resources include water treatment services companies, equipment suppliers,
and mechanical contractors. In some cases, facilities may use outsourcing for
procurement of all industrial water treatment chemicals and associated services. This
section addresses some of the options for developing both a water treatment program
and performance standards that apply to implementation of the program.
Problems can occur when water treatment programs are not developed properly. Each
water treatment program is designed to address regulatory compliance and safety
requirements as well as water quality and equipment protection. A potential
consequence of inadequate planning and design of a water treatment program is
preparing inadequate scopes of work for use in procuring (contracting) for services. If
equipment protection is not adequate, the cost attributed to this failure often far
outweighs the cost of the water treatment chemical program. The most obvious problem
is damage to, or the need for premature replacement of, the water-contacted
equipment. Loss of operational efficiency is also a problem but is not always as
3.2 OPTIONS FOR SETTING UP A WATER TREATMENT PROGRAM. There are four
methods for developing and implementing a water treatment program:
3.1 QUALIFICATIONS. The SOW specifies the minimum qualification requirements for
contractors and contractor representatives. These requirements are developed to allow
the participation of qualified contractors (water treatment chemical companies) having
national, regional, and local operations. The SOW can specify the minimum number of
years that the company has been in business and the minimum number of years and
type of experience of contractor representatives, as well as required technical service
capabilities.
3.2 SUBMITTAL REQUIREMENTS AND FORMAT. The SOW clearly specifies the type
of response (submittal) that is required from an RFP or RFB. This is necessary to avoid
receiving bid responses that are so different in their presentation that they cannot be
easily or objectively compared. The evaluation process can be simplified by requiring
bidders to provide a comprehensive acknowledgement that they understand and accept
all requirements for compliance, qualifications, service requirements, and performance
standards. The RFP/RFB should require a simple, generic, technical summary that lists
the proposed chemical technology and treatment ranges for each type of system to be
serviced under the procurement.
3.3 WATER QUALITY. The water supplied as makeup to industrial water systems is
characterized in terms of its source, treatment, and quality, including seasonal and
temporal variances. If external treatment is used on individual systems such as a steam
boiler, this treatment is identified.
3.8 CHEMICALS AND TEST EQUIPMENT. The SOW specifies any restrictions on the
use or discharge of chemicals. Examples of restrictions can include limitations on the
use of acid, shipping container size limits, microbiocide selection criteria, and limitation
on use of dry chemicals.
3.9 QUOTATION FOR COST AND USAGE. The SOW specifies how the cost of
chemicals and services is being calculated and quoted. For example, quotations for
chemical treatment can be based on the cost to treat 3.785 cubic meters of water. Cost
for services in the SOW can be required to be included in the cost of chemical treatment
or quoted separately as line items, time, and materials. Contracts that require a "not-to-
exceed" quotation supply bidders with a not-to-exceed water usage estimate.
4. REPORTS AND AUDITS. Reports and audits are tools for documenting
performance and cost effectiveness of any industrial water treatment program. Audits
serve to verify results from the water treatment service company. Audits also serve to
verify the cost-effectiveness of product being supplied by the water treatment service
company. Audits are performed by appropriate agencies or by independent consultants
contracted to perform such duties.
5. GLOSSARY
Acid — A compound, usually having a sour taste, which can neutralize an alkali or
base; a substance that dissolves in water with a formation of hydrogen ions.
Aeration — Intimate contact between air and liquid by one of the following methods:
spraying the liquid in the air; bubbling air through the liquid; or agitating the liquid to
promote surface absorption of air.
Algae — Tiny plant life, usually microscopic, existing in water. They are mostly green,
blue-green, or yellow-green, and are the cause of most tastes and odors in water. They
create suspended solids (SS) when they grow in an industrial water system.
Alkalinity — (a) A term used to represent the content of carbonates, bicarbonates,
hydroxides, and occasionally borates, silicates, and phosphates in water. (b) The
capacity of water to react with hydrogen ions.
Alkalinity, total or mixed indicator (M) — A measure of the total alkalinity of water.
Measured by the quantity of 0.02 normality (N) sulfuric acid required to bring water to
pH of 4.4, as indicated by the change in color of methyl orange or a mixed indicator.
Results are expressed in parts per million (ppm) as calcium carbonate.
Alkalinity, Phenolphthalein (P) — A measure of hydroxide ions (OH) plus one-half of
the normal carbonates in water. Measured by the quantity of 0.02 normality (N) sulfuric
acid required to bring the water to pH 8.2, as indicated by the de-colorization of
phenolphthalein indicator. Results are expressed in parts per million (ppm) as calcium
carbonate.
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Alkalinity, Hydroxyl — A measure of hydroxyl ion (OH ) contribution to the alkalinity.
This is related to the system pH and also may be referred to as “causticity.”
Bacteria — Simple single-cell microscopic organisms generally free of pigment. They
do not require light for their life processes.
Backwash — The reversal of flow through a filter or an ion exchanger to wash clogging
material out of the filtering medium and reduce conditions causing loss of head.
Backflow preventer — A device for a water supply pipe to prevent the backflow of
water into the water supply system from the system which it supplies.
Base — An alkali or hydroxide of alkali metals and ammonia. They can neutralize acids
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to form salts and water. A base will ionize to form hydroxyl ions (OH ).
Biocides — Material typically used to destroy microorganisms (also called
“microbiocides”).
Biological Deposits — Water-formed deposits of organisms or the product of their life
processes. Biological deposits may be composed of microscopic organisms, as in
slimes, or of macroscopic organisms such as barnacles or mussels.
Blowdown — Draining a portion of water from a system to reduce the concentration of
dissolved solids or to discharge accumulations of materials carried by the water.
British Thermal Unit (BTU) — The amount of heat necessary to raise the temperature
of one pound of water one degree Fahrenheit (°F).
Brine — A saturated solution for ion exchange regeneration, refrigeration, or cooling
processes. It is usually a sodium chloride water solution for ion exchange regeneration.
It may be sodium chloride water solution or calcium chloride water solution for
refrigeration.
Causticity — A common term that describes hydroxyl alkalinity or the alkalinity
resulting from the presence of the hydroxyl ion (OH).
Concentration — A measure of the amount of dissolved substances contained per unit
volume of solution. This may be expressed as grains per gallon, pounds per million
gallons, milligrams per liter, ppm, or percent.
Condensate — The material formed when vapor returns to the liquid state. In steam
heating systems, the water condensed from steam. In air conditioning, water extracted
from air by condensation on the cooling coil of a refrigeration machine.
Conductivity, Specific Conductance — The reciprocal of the resistance in ohms
measured between opposite faces of a centimeter cube of an aqueous solution at a
specified temperature. Electrical conductivity is expressed in micromhos (µmhos), the
reciprocal of megohms. This is used as a measure of total dissolved solids (TDS).
Corrosion — The destruction of a substance, usually a metal, or its properties because
of a reaction with its (environmental) surroundings.
Disinfection — The process of killing most (but not necessarily all) of the harmful and
objectionable microorganisms in a fluid by various agents such as chemicals, heat,
ultraviolet light, ultrasonic waves, or radiation.
Cycles of Concentration (COC) — In a system in which water lost through evaporation
and blowdown is replaced with makeup water, COC is the ratio of the makeup quantity
to the blowdown quantity (COC = M/B). It is the number of times the makeup water is
concentrated in the system. The COC can also be calculated by dividing either the
conductivity or the chloride content of the blowdown by the conductivity or chloride
content of the makeup (COC = Condbd/Condmw).
Deaerator — Device for removing non-condensable gases from the boiler. It may
operate on the principle of either heat or vacuum.
Dealkalization — Exchange of bicarbonate for chlorides in an ion exchange process.
Deionization — Complete removal of ions from water.
Demineralization — Reduction of the mineral content of water by a physical or
chemical process; removal of salts.
Dissolved solids — (a) Solids, usually minerals, which are present in solution. (b) The
dried residue from evaporation of the filtrate after separation of suspended solids (SS).
Distribution Ratio (D.R.) — This is a measure of the vapor/liquid ratio for a given
material. Extremely high and low values are generally unadvisable. A high D.R. results
in either high amine losses at any vents or little availability of amine at points of initial
condensation, or both. A low D.R. results in high amine losses in the blowdown.
Evaporation — The process by which water passes from a liquid state to a vapor. It is
the main process by which heat is removed from a cooling tower and steam is produced
in a boiler.
Feedwater — Water being applied to the feedwater heater or to the boiler, consisting of
both makeup and condensate return.
Filming Amines — Chemicals that form an impervious barrier between metal and the
steam condensate to prevent corrosion.
Foulants — Deposition of materials normally in suspension. This includes silt, air-
scrubbed dust, microbiological residuals, reaction products from treatment, and
corrosion products.
pHs — The pH of saturation. It is the pH value below which a material will go into
solution (dissolve) and above which it will precipitate. It is applied to calcium carbonate
in the Langelier, Ryznar, and Practical Scaling Indices. It is a function of the calcium
hardness, the total alkalinity, the total dissolved solids (TDS) and the temperature. It is
determined with graphs, tables, or special slide rules. This equation is useful:
pHs = 12.27 - 0.00915T - log CaH - log TA + (log TDS)/10.
Phosphates — Chemicals used for corrosion control in cooling towers and deposit
control in boilers. Commonly, these occur as orthophosphates or polyphosphates. The
level of the active phosphate chemical is reported either as percent P2O5 (phosphorus
pentoxide) or as PO4 (phosphate), with these two oxides of phosphate being related by
factor as follows: PO4 = 1.34 x P2O5.
ppm — Parts per million; one pound of material dissolved in one million pounds of
water.
Precipitate — (a) To separate a dissolved substance in the solid form by its removal
from a solution. (b) The substance in solid form that has been separated from solution.
Practical Scaling Index (PSI) — A modified scaling index developed by P.R. Puckorius
and J.M. Brooke to provide a better and more consistent indication of scaling conditions
of cooling water. It is based on using the pH of equilibrium (pHeq) rather than the actual
pH, and is calculated as follows:
PSI = 2 pHs - pHeq.
As with the RSI, a value less than 6.0 in natural water indicates a scale-forming
tendency. A value greater than 6.0 in natural water indicates a scale-dissolving
tendency.
Regeneration — That part of the operating cycle of an ion exchange process in which a
specific chemical solution is passed through the ion exchange bed to prepare it for a
service run (i.e., return the ion exchange bed to its original composition).
Ryznar Index (stability index) — An index classifying water as to its ability to dissolve
or deposit calcium carbonate scale. It is calculated as twice the pH of saturation minus
the actual pH (RI = 2 pHs - pH). Although in theory an RI of 7.0 should be neutral,
experiments indicate that 6.0 is a better value. A value less than 6.0 in natural water
indicates a scale-forming tendency. A value greater than 6.0 in natural water indicates a
scale-dissolving tendency.
Scale — Deposition on a heat transfer surface of normally soluble salts. Scale is usually
crystalline and dense, frequently laminated, and occasionally columnar in structure.
Shock Feed — The process of adding one or more water treatment chemicals in one
application rather than gradually.
Slime — Biological growths that may accumulate to the extent that they foul equipment.
Sludge — A water-formed deposit that will settle, and may include all suspended solids
(SS) carried by water. Sludge is commonly formed in boilers where it may be baked into
place and become hard and adherent.
Softening Water — The process of removing from water the mineral substances that
produce a condition called hardness. There are two softening processes in general use:
chemical precipitation (lime and lime/soda softening) and the zeolite ion exchange
process.
Solids, Suspended (SS) — All matter in water that is not dissolved and can be
removed with filtration.
Solids, Dissolved — The total concentration of all substances in a filtered solution
which exist as solids after the liquid is completely evaporated from the solution.
Solids, Total — The sum of the suspended and dissolved matter (solids).
Zeolite — Natural minerals as well as synthetic resins used for ion exchange.