Engineering Encyclopedia

Saudi Aramco DeskTop Standards

Exxon Chemical And Mechanical Cleaning Manual

6) Precommission Cleaning And Passivation

Note: The source of the technical material in this volume is the Exxon Research
and Engineering Company Chemical and Mechanical Cleaning Manual.
Warning: This Exxon Research and Engineering Company Chemical and
Mechanical Cleaning Manual is made available exclusively for the use of
Saudi Aramco for its own use and for no other purpose. The disclosure of its
content are subject to the provisions of the Contract No. 30934/00 dated
November 1, 1986. The material in this manual may not be copied,
reproduced, sold, given, or disclosed to third parties or otherwise used in
whole or part without the written permission of the Vice President,
Engineering Services, Saudi Aramco.

Chapter : Precommission Cleaning And Passivation For additional information on this subject, contact
File Reference: Section 6 R.S. Sarathy on 875-3520
Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

TABLE OF CONTENTS

I. EQUIPMENT ENCOMPASSED IN BASIC PRACTICE 18-8-1 ...................................... 1

General Procedure..................................................................................................... 1

Cleaning Requirements Depend on Service ............................................................... 2

Precautions to be Followed During Cleaning............................................................. 3

Tables with Step Procedures ..................................................................................... 4

II. PRECLEANING AND PASSIVATION OF COOLING WATER SYSTEMS ................. 9

Why is Pretreatment Necessary ................................................................................. 9

The Benefits of Pretreatment....................................................................................10

Phosphate-Surfactant-Dispersant is Typical First Step..............................................10

Second Step: Completing the Passivation with High Inhibitor Dosages ....................11

Saudi Aramco DeskTop Standards

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

I. EQUIPMENT ENCOMPASSED IN BASIC PRACTICE 18-8-1

Some equipment must be precommission cleaned to remove dirt, mill scale, and other
contaminants which are present oil metal surfaces after fabrication. If not removed these
particles can dislodge and damage or plug critical sections of the equipment. Generally, the
following systems are precommission cleaned as required by BP18-8-1. This Basic Practice
should be applied when contracting a job or preparing a specification.

• Steam generators (boilers, feedwater piping, superheaters)

• Steam turbine inlet piping
• Compressor suction and interstage systems
• Lube and seal oil systems
• Positive displacement pumps

Boiler feedwater piping downstream of the deaerator is cleaned to remove scale or dirt which
could later dislodge and foul boiler tubes. The heat transfer sections of boilers are cleaned to
obtain clean metal surfaces for efficient heat transfer. Compressor suction and interstage
systems and steam turbine inlet piping are cleaned to remove particles which may otherwise be
carried into the turbine or compressor and damage the blading. Lube and seal oil systems are
cleaned to avoid plugging of the narrow orifices in these systems. Positive displacement pumps
require cleaning to avoid scoring the cylinder walls with loose particles.

General Procedure

The normal procedure for precommission cleaning involves:

• Flushing with fresh water to remove loose dirt

• Alkaline detergent wash to remove oil and grease
• Solvent cleaning with acid or chelants to remove rust and mill scale
• Post cleaning passivation to prevent after-cleaning corrosion

The required steps are indicated in Table A.

Steam generating equipment is washed with a dilute Na2CO3 and Na3PO4 solution containing
detergent. An NaOH solution is used for the alkaline washing of piping systems. Specific
procedures are given in Table 1.

Saudi Aramco DeskTop Standards 1

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

Inhibited 6% hydrochloric acid is most frequently used for pickling ferrous equipment because it
is cheap and easily handled. Table 2 gives the specific procedures for acid cleaning piping
systems. Table 3 outlines the procedures for acid cleaning steam generating equipment.
Alternative procedures for cleaning with ammoniated citric acid solutions and with chelating
agents are also included in Table 3. One of these alternative cleaning solutions is used when
hydrochloric acid is not suitable.

Caustic or phosphoric acid solution is used for post cleaning passivation of piping systems.
Steam generating equipment is passivated. with hydrazine. Table 4 lists two recommended
procedures for post cleaning passivation.

Cleaning Requirements Depend on Service

The outlet steam pressure determines the extent of cleaning necessary for steam generator
equipment. For low pressure generators (less than 450 psi or 31 kg/cm2) flushing with clean
water followed by an alkaline detergent wash is sufficient. Higher pressure generators (450-
1800 psi or 31-124 kg/cm2) require a water flush, alkaline wash, acid cleaning, and passivation.

The cleaning procedure required for compressors depends on the type. Centrifugal and axial
compressors suction sections require only flushing with clean water. Reciprocating and rotary
compressor suction and interstage sections need a more extensive program, similar to the
program for high pressure steam generators.

Cleaning requirements for steam turbine inlet piping is determined by the steam pressure carried.
Low pressure piping (below 625 psig or 43 kg/cm2) can be cleaned with only a steam blow to
remove loose scale and dirt. High pressure piping (above 625 psig) requires a full program of
flushing, alkaline wash, acid cleaning, and passivation.

Both lube and seal oil systems and positive displacement pump suction sections require
extensive cleaning, similar to the program recommended for high pressure steam turbine inlet
piping. Simple water flushing is not sufficient for cleaning these systems. This is because the
narrow orifices in the lube and seal oil systems can be plugged by small amounts of scale or dirt.
Likewise small amounts of dirt will score the cylinder walls of positive displacement pumps.

Saudi Aramco DeskTop Standards 2

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

Precautions to be Followed During Cleaning

Certain precautions must be followed during cleaning to avoid corrosion of the equipment. For
instance, stagnant solutions can cause pitting of the equipment. Therefore, equipment should
have low point drains and high point vents so that the equipment can be filled and drained easily.
Drains should be sized to allow complete draining of the equipment in less than two hours. Also,
heat should not be applied directly to the equipment being cleaned since this will cause high
metal temperatures and increase corrosion. The solution should be heated externally to the
equipment and then pumped through the equipment. treating the solution external to the
equipment will also result in better control of the solution temperature during the cleaning
operation.

Equipment which contains austenitic stainless steels cannot be cleaned with inhibited
hydrochloric acid. Chloride ions will cause stress corrosion cracking (SCC) of austenitic steels.
Ammoniated citric acid or chelating agents should be used in these cases. Also the chloride
content of the solutions used in cleaning austenitic equipment should not exceed 25 ppm.
Additional precautions for review when considering chemical cleaning with HCl, citric acid, or
EDTA are covered in Section 7 - Post Service Cleaning of Steam Boilers. Specific inspection
and testing requirements to minimize corrosion during cleaning are indicated also in BPI8-8-1,
paragraphs 5.1 to 5.5.

Saudi Aramco DeskTop Standards 3

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

Tables with Step Procedures

Table A - Cleaning Requirements and Methods
The degree of cleaning and surface preparation required, and acceptable methods to accomplish this are
specified below:
EQUIPMENT DEGREE OF CLEANING AND ACCEPTABLE METHODS
SURFACE PREPARATION (Step Procedure in order given)
Piping Systems (Carbon and Low Alloy Steels <
5Cr):
Lube and Seal Oil Systems (field fabricated A, B, C, D 3, 4, 5, 6
piping only)
Centrifugal and Axial Compressor Suction A 2
Reciprocating and Rotary Compressor Suction
and Interstage (including vessels, exchangers, A, B, C, D 1 or 2, 7
and pulsation suppression devices or
Power Displacement Pumps Suction 3, 4, 5, 6
Steam Turbine Inlet: >625 psig A, B, C, D 3, 4, 5, 6
>625 psig A 8
Steam Outlet Pressure, psig Steam Outlet Pressure, psig
Steam Generating Equipment: <450 450 - 1800 <450 450-1800
Feed Water Line Downstream of Deaerator A A, B, C, D 3 3, 4, 5, 6
Steam Generator A, B A, B, C, D 3, 4 3, 4, 5, 6
Superheater, Drainable and Ventable A, B A, B, C, D 1, 3 or 3, 4 3, 4, 5, 6
or 1, 3, 8
Superheater, Non-Drainable and A, B A, B, C 1, 3, 8 1, 3, 8
Non-Ventable

Note: Symbols used in the above table are:

A. Removal of all loose non-adherent materials together with all adherent material which could break away during
operation of the equipment.
B. Removal of oil, greases and protective coatings.
C. Removal of adherent rust and mill scale to leave bare metal.
D. Protection of surface to prevent rust bloom following cleaning and prior to start-up.

(STEP PROCEDURE IN ORDER GIVEN)

1. Clean construction techniques:
For compressor and positive displacement pump piping prior to fabrication:
Sand or grit blasting for rust and scale removal together with “clean” weld techniques (TIG, MIG, etc.) for all closing welds.

For steam generators this includes use of cold drawn tubing and cold bending.
2. Post fabrication mechanical cleaning:
Grinding, pigging, or sand or grit blasting.
3. Flushing with fresh clean water to remove trash and debris.
4. Alkaline detergent wash for oil and grease removal. See Table 1.
5. Solvent cleaning with acids or chelants, for rust and mill scale removal. See Table 2 for Piping Systems, (hydrochloric acid)
and Table 3 for Steam Generating Equipment (hydrochloric acid, citric acid, or chelants). If ammoniated citric acid or chelating
agents are used per Table 3 procedures, further passivation is not required.
6. Post cleaning passivation:
Prevention of after-rusting of cleaned surfaces by chemical treatment. See Table 4.
7. Post cleaning protection:
Vapor phase inhibitor; or, coating with a lubricant compatible rust preventive except for non-lubricated compressors and those
in refrigeration service. Blind, plug or cap all piping joints left temporarily disconnected.
8. Steam blow to ensure removal of loose scale.

Acceptable Metric Equivalents

psig 450 625 1800
kPa 3100 4300 12500

Saudi Aramco DeskTop Standards 4

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

TABLE 1 - Alkaline Detergent Wash for Oil and Grease Removal

(Step Procedure in order given.)

(2)
STEAM GENERATING EQUIPMENT

1. Backflush superheater tubes into the steam drum using steam condensate or other low solids water.
2. Fill boiler (and economizer if present) to normal operating level with solution containing 0.5% Na2CO3, 0.5% Na2CO4
and 0.05 to 0.1% wt. Non-ionic detergent.
3. Fire boiler to raise pressure to 300 psig or 1/5 of operating pressure whichever is less. Hold pressure for 4 hours.
4. After 4 hours shut down boiler and let pressure drop by at least 10 percent. Blowdown boiler using all bottom
blowdown valves in sequence. Restore normal operating level after blowing.
5. Check samples periodically for alkalinity and phosphate. If concentration drops below 0.25%, add more chemicals
to restore the levels specified in Step 2.
6. Repeat Steps 3 and 4 at least two more times or until samples indicate that oils and siliceous materials have been
removed.
7. When samples show no further pickup or oil, shut off burners. After drum pressure drops below 25 psig, open
drum vents and superheater drains. When steam drum temperature drops below 200°F, drain boiler.
8. Backflush superheater into steam drum for about 20 minutes. Fill with rinse water heated to 150°F minimum, then
drain boiler.
9. Allow boiler to cool, open and inspect.

(1) (2)
PIPING SYSTEMS

1. Fill equipment with alkaline solution containing 3% NaOH, 1% sodium metasilicate, 1% trisodium phosphate and
0.1% non-ionic detergent.
2. Heat solution to 160 to 180°F and circulate intermittently for at least 6 hours.
3. Drain system and flush with fresh water until the effluent pH is less than 8.

NOTES: (1) The following facilities are required:

a. Provision to isolate the equipment to be cleaned.
b. Vents at all high points, drains at all low points, so that the system can be filled and drained completely.
(2) All percentages are expressed as weight percent unless otherwise specified.

TABLE 2 - Solvent Cleaning for Rust and Mill Scale Removal Procedures Piping Systems (3)

(Step Procedure in order given.)

(1) (2) (4)
INHIBITED HYDROCHLORIC ACID

1. Fill system with 6% hydrochloric acid containing 0.25% ammonium bi-flouride inhibited with 2 gals per 1000 gals
Armohib 28, Rodine 213 or equivalent.
2. Heat solution to 160°F and circulate for at least 15 minutes each hour for a minimum of six hours or until reaction
is complete.
3. Take samples at least once per hour following circulation and test for acid strength and total iron concentration. If
acid concentration drops below 3% add acid to bring concentration to 5%. Continue cleaning until iron and acid
concentrations reach equilibrium.
4. Drain system and flush with potable water (to which 0.1% citric acid may be added to reduce after rusting).
5. Neutralize and passivate system with 1% soda ash and 0.5% sodium nitrite solution.
6. Drain system, open and inspect.

NOTES: (1) Use of inhibited hydrochloric acid is acceptable for carbon and low alloy steels. It is not acceptable for
systems containing stainless or high alloy steels.
(2) The following facilities are required:
a. Provision to isolate the equipment to be cleaned.
b. Vents at all high points, drains at all low points, so that the system can be filled and drained completely.
(3) Where piping systems can be readily cleaned by vapor techniques, or with chelants, proposals to use such
methods shall be submitted to purchaser for approval by Owner’s Engineer.
(4) All percentages are expressed as weight percent unless otherwise specified.

Saudi Aramco DeskTop Standards 5

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

TABLE 3 - Solvent Cleaning for Rust and Mill Scale Removal Steam Generating Equipment

(Step Procedure in order given.)

(1) (2) (5)
INHIBITED HYDROCHLORIC ACID

1. Fill superheaters and economizers with condensate or other low solids water, and maintain water “wedge” during
remainder of cleaning operation.
2. Fill boiler with water heated to 180°F or alternatively fill boiler with water and inject steam to bring temperature to
180°F. When metal temperatures have reached 180°F drain boiler. Close all furnace openings and dampers to
retain heat.
3. Open drum vent valves. Close boiler blowdown and chemical valves. Isolate all other valves not being used for
circulation.
4. a) Fill boiler to normal liquid level with 6 percent inhibited hydrochloric acid solution containing 0.25% by wt.
Ammonium bifluoride heated to 170°F by blending the dilution water with steam. Inhibitor shall be Armohib 28,
Rodine 213 or equivalent in concentrations of 2 gal per 1000 gal of boiler capacity. (Inhibitor effectiveness should
be confirmed by test.)
b.) Alternatively, hot water may be withdrawn from the boiler, pumped through a mixing header to provide no
more than 10 percent concentration and returned to the steam drum. In this case it is recommended that at
least half of the required inhibitor shall be added to the water prior to acid injection.
5. Solution shall be circulated for 15 minutes each hour for at least six hours. Samples shall be taken each hour
following circulation and tested for acid strength and total iron concentration. Cleaning is continued until acid
strength and total iron concentration reach equilibrium. If acid concentration drops below 3% add additional acid
to bring concentration to 5%.
6. Drain acid solution under nitrogen pressure.
7. Fill water to high water level in drum with water heated to 150°F. Simultaneously back flush superheater with
condensate or low solids water into steam drum. Drain boiler.
8. Refill boiler with clear water containing 0.1% citric acid at 150°F. Circulate 1 hour. Drain under nitrogen pressure.
9. Fill boiler to normal operating level with a neutralizing solution containing 1% by wt. soda ash (Na2CO3). Fire
boiler and bring pressure to 100 psig and hold for 2 hours. Allow boiler to cool to less than 200°F, then drain.
10. Allow boiler to cool, open and inspect.
(3) (5)
AMMONIATED CITRIC ACID
1. Fill boiler with water and heat to 200°F (superheater shall be flooded with condensate prior to filling).
2. Add inhibitor equivalent to Rodine 31A (or Armohib 31) at a rate of 0.1% or as prescribed by inhibitor
manufacturer, whichever is more, to the water in the boiler prior to the addition of citric acid.
3. Add enough ammoniated citric acid solution (pH 3 to 3.5) to make 3% solution in the boiler. Circulate until mixing
is complete. (A preferred alternative is to blend ammoniated citric acid solution, water, inhibitor and steam to
make a 3% solution at 180°F for injection into a preheater boiler.)
4. Circulate until reaction is complete - but not less than 4 hours. Completion is indicated when acid concentration
and iron content in the solution as determined by titration have been constant for at least one hour. If solution
concentration drops below 1%, add ammoniated citric acid to raise concentration to at least 2%.
5. Add additional ammoniated citric acid solution equivalent to 0.5% in the boiler. Boiler should be about 150°F .
6. Inject ammonia to raise the pH of the solution in the boiler to 9.5. This should require about 1% anhydrous
ammonia based upon the total wt. of solution in the boiler. Circulate for four hours, then drain boiler.
7. Add sodium nitrite to produce 0.5% solution in the boiler. Circulate for four hours, then drain boiler.
8. Rinse boiler at least twice with clear water heated to 150°F. Drain boiler.
9. Allow boiler to cool, open and inspect.

NOTE: (Table 3 and notes continued on next page.)

Saudi Aramco DeskTop Standards 6

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

TABLE 3 - Solvent Cleaning for Rust and Mill Scale Removal Steam Generating Equipment (Cont’d)

(4) (5)
CHELATING AGENTS

1. Fill boiler and fire to bring temperature to about 250°F. Drop level in the steam drum to make room for cleaning
solvent.
2. Dilute sufficient inhibitor (Dow-A-196 or Halliburton OSI-1) with water to make a 0.1% solution in the boiler, and
add to boiler via the chemical addition line. Wait 30 min. for thermal mixing.
3. Pump in sufficient chelant to make a minimum 4% chelant concentration (10% max.) by wt. in the boiler. Adjust
level in boiler to normal level.
4. Isolate the system, but make certain the superheater is protected by venting to avoid overheating of tubes.
(Note: Vapor will contain noxious ammonia fumes.)
5. Fire boiler to raise pressure to 80 psig [Temperature not to exceed 325°F (163°C)]. Stop firing, leave fans on at
low speed, and allow pressure to drop to 20 psig.
6. Sample and titrate at least once per hour for available chelant and for iron.
7. Repeat Step 5 until concentration of chelant and iron stabilize. If chelant concentration drops below 1%, add
sufficient chelant to bring concentration to 3%. Job is complete when titration shows stable chelant
concentration with no further increase in iron. Total time required may be 12 to 18 hours. The pH during cleaning
should be about 9.2 to 9.5. If the pH drops below 9.0, add ammonia to raise the pH to about 9.2 to 9.5.
8. Cool boiler to less than 200°F and drain under nitrogen pressure.
9. Backflush superheater with condensate into the steam drum for 20 minutes to insure removal of any entrained
chemical. Fill boiler to high level with clean water containing 100 ppm hydrazine at 180°F.
10. Drain under nitrogen pressure.
11. Allow boiler to cool, open and inspect.

Notes:
(1) Use of inhibited hydrochloric acid is acceptable provided the boiler can be properly isolated from instrument leads,
etc.
(2) The following facilities are required:
a. A 2 in. NPS (50 mm) or larger acid fill and drain connection to the stream and mud drums.
b. Hot water or steam heating line with facility to regulate temperature between 150 and 180°F at location near
boiler.
c. An atmosphere vent line and a nitrogen fill line on the steam drum.
(3) Use of Ammoniated Citric Acid per the procedure specified in the citrosolve process licensed by Chas. Pfizer & Co. is
acceptable.
(4) Use of chelants of the type represented by the ammonium salt of ethylenediaminetetraacetic acid (Dow Vertan 675 or
Halliburton Macor) is acceptable.
(5) All percentages are expressed as weight percent unless otherwise specified.

General Note: Armohib is a trademark of ARMAK Co.

Macor is a trademark of Halliburton Services.
Rodine is a trademark of AMCHEM Products Inc.
Vertan is a trademark of Dow Chemical Co.

Saudi Aramco DeskTop Standards 7

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

TABLE 4 - Post Cleaning Passivation

(Step procedure in order given.)

(1) (3)
PIPING

1. Circulate a solution of either:

(a) 2 to 5 percent phosphoric acid at 180°F for 1 hour.
(b) 1% caustic and 0.5% sodium nitrite at 180°F for 2 hours.
2. Drain and air dry.
3. When the time between cleaning and start-up exceeds 10 days. Steps 1a and 2 shall be used followed by
plugging all openings and pressurizing at 5 to 10 psig of nitrogen.
(2)
STEAM GENERATING EQUIPMENT
1. Fill with potable water containing 200 ppm hydrazine adjusted to pH 10.5 with ammonia.
2. Fire boiler to raise pressure to 100 psig and hold for 4 hours.
3. Allow boiler to cool and purge with nitrogen to eliminate air.
4. Maintain boiler under 5 psig nitrogen pressure until start-up.

Notes:
(1) Piping must be flushed free of alkaline deposits and air dried prior to commissioning.
(2) (a) Boiler may be fired as required to prevent freezing.
(b) Boiler may be started without draining passivation solution, provided steam is vented at the boiler until
hydrazine content of boiler water is approximately 1 ppm.
(3) All percentages are expressed in weight percent unless otherwise specified.

Saudi Aramco DeskTop Standards 8

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

II. PRECLEANING AND PASSIVATION OF COOLING WATER SYSTEMS

Why is Pretreatment Necessary

Oil, grease, lubricants and other foreign matter introduced during construction, and mill scale,
are always present on metal surfaces in new cooling water systems. These materials prevent the
essential contact between a corrosion inhibitor and the metal surface, creating gaps in the
inhibitor film. This is particularly a problem with today's generation of non-chromate inhibitors
which develop fragile films even on clean surfaces. The end result is the initiation of pitting
corrosion under mounds of corrosion product called tubercules.

To avoid this problem, a system should be cleaned prior to start-up to accept the corrosion
inhibitor. Once a system is cleaned, metal surfaces are highly reactive. In this state, corrosion
sites can form rapidly wherever oxygenated water contacts the clean, active metal. Therefore,
metal surfaces (exchanger tubes and piping) must be conditioned chemically so that a protective
surface film forms to inhibit corrosion. This is the second function of pretreatment called
passivation. It cannot be achieved easily by the normal application of chemical treatment after
start-up because the continuous, low treatment levels used can only heal slight breaks in the film
that may occur from adverse chemical and mechanical factors in the system; the maintenance
dosage of chemicals is not designed to establish passivation in previously untreated systems.

ERE Report EE.19E.82, Precleaning and Passivation Cooling Water Systems, provides
guidelines on:

• Pretreatment - a combination cleaning and passivation of a new systems which removes

oils, greases and residues, and establishes a uniform, tightly adherent, protective film. It
consists of two parts:
- Using selected phosphate-detergent solutions which clean and partially passivate
metal surfaces.
- Followed by high start-up dosages of corrosion inhibitor to complete the passivation.
• Passivation - treating an existing cooling water system or individual exchangers after an
inadvertent acid spill, after chemical or mechanical cleaning, and/or after an extended
turnaround (see Section 12).

Saudi Aramco DeskTop Standards 9

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

The Benefits of Pretreatment

Report EE.19E.82 summarizes the available data on reductions in corrosion and. Fouling factor.
These are as follows:

• Lack of pretreatment may result in tuberculation, pitting corrosion and iron fouling of
heat exchange equipment, and provide a poor foundation for chemical treatment.
• Pretreatment can reduce fouling factor by 40%. In addition, corrosion rates for carbon
steel will be reduced 35-70% and for Admiralty brass by 45-90% during the fist several
months of operation.
• Pretreatment can extend the trouble-free (limited fouling and corrosion) operation of
carbon steel heat exchanger tubes as much as 3-5 years (Baytown Refinery data).

Phosphate-Surfactant-Dispersant is Typical First Step

Cleaning is the first step in pretreatment, followed by passivation. Many vendors recommend a
one-step approach in order to save time and to minimize the quantity of effluent. This of course,
makes compromises since oil and iron removal, and passivation, are best done in different pH
ranges. Most one or multiple step treatments utilize phosphates and surfactants which provide a
mild cleaning and passivation. Typically, 200-300 ppm PO4 in the form of alkaline sodium
tripolyphosphate or tetrasodium pyrophosphate is circulated through the entire system or
individual exchangers after the main headers have been flushed of large debris. Circulation is
preferred to soaking. As much as 400-1000 ppm PO4 has been used to reduce cleaning time.
Phosphates dissolve light rust and fabrication oils, and, at the same time, passivate the metal
surfaces. A high dosage is required to remove rust, to speed the passivation process and to
compensate for adsorption onto metal surfaces.

In addition to phosphate, a non-ionic or anionic surfactant, and a dispersant or sequestering agent

is added roughly in the ratio of 90% sodium phosphate to 10% surfactant. The surfactant should
have a low foaming tendence. Anti-foam and a copper complexer like tolyltriazole are also
frequently used, as required. Surfactants help to remove hydrophobic materials by reducing the
surface tension of water and permitting better penetration into deposits. They also reduce the
laminar layer, permitting turbulence to keep suspended solids in circulation. Dispersants and
sequestering agents are added to prevent deposition of iron and calcium orthophosphate and to
keep charged particles (clay, silt) from agglomerating. Low molecular weight (1000-3000)
polyacrylates (5-20 ppm active), HEDP (5-15 ppm active), and certain hydroxylated
polymethacrylate polymers (60 ppm as product) are commonly used. In very hard water,
polymaleic acid dispersants and hydroxylated polymethacrylate polymers should be considered
to disperse calcium orthophosphate.

Saudi Aramco DeskTop Standards 10

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

A silicone-based anti-foam may be required to reduce foaming created by the high concentration
of surfactant. A copper complexer (benzotriazole or tolyltriazole) at a dosage of 2-5 ppm active
ingredient complexes any residual copper entering from cooling tower lumber and exchanger
gasket lubrication. It also helps to passivate copper-bearing alloys by adsorbing onto the
surfaces of these metals.

All the above chemicals are slug-fed to the system in an area of good water flow, with the
quantity of chemical based on the volume of the system. Cost can be reduced by operating the
cooling tower at its lowest permissible water level to minimize dilution. Circulation time
depends on the concentration of chemicals used, temperature and initial degree of cleanliness.
Generally, circulation is continued for 3-4 days and is followed by heavy blowdown. Circulation
somewhat longer than 4 days is acceptable only at ambient temperatures and when calcium
hardness exceeds 100 ppm as CaCO3 (for corrosion protection). Blowdown rate may be limited
by the ability of the wastewater treatment plant to absorb extra contaminants. Temperature of
120°F (49°C) helps speed the cleaning job to under 2 days. During circulation, velocity should
be maximized by operating all cooling tower pumps.

During pretreatment, pH control is required. Recommendations for optimum pH depend on the

supplier chosen and his choice of chemicals. In general, a range of pH 6.5-7.5 is common. This
permits adequate oil removal and allows a thin iron-calcium phosphate film to form on the
surface. Only loose iron oxides will be removed at this pH because removal of tenacious iron
deposits is possible only at lower pH (below 4.5) with these chemicals. However, low pH
increases the corrosion potential, and may also decrease the removal rate of oil. High pH (8-9)
may improve oil removal by emulsification, but may cause the precipitation of calcium
orthophosphate. The shorter the cleaning time, the less the risk. High pH can be used in a one-
step pretreatment provided care is taken to analyze the water frequently so that calcium
orthophosphate solubility is not exceeded. This may require using blowdown to stay below the
solubility limit and there may incur greater effluent and chemical treatment costs. High pH can
also be considered in a multi-step orientation prior to the introduction of phosphate. However,
knowledge of the surfactant used is important because some (such as Cyanamid’s Aerosol OT,
an anionic surfactant) work best at neutral pH and do not require alkaline conditions to remove
oil. Multi-step operations may do a better job but require more chemicals and result in a larger
disposal problem.

Saudi Aramco DeskTop Standards 11

Engineering Encyclopedia Exxon Chemical And Mechanical Cleaning Manual
Section 6
Precommission Cleaning And Passivation

Second Step: Completing the Passivation with High Inhibitor Dosages

After the phosphate-surfactant and any other chemicals used to preheat the system are eliminated
by heavy blowdown, a transition to the normal chemical treatment program follows. Initially, a
higher dosage of corrosion inhibitor is required because:

• There is a system demand for inhibitor as it is adsorbed onto metal surfaces.

• A higher dosage heals breaks in the passive film established during the first step.
• Complete passivation is quicker if a higher inhibitor dosage is used.

Since many inhibitor programs are now in use, Report EE.19E.82 provides recommendations for
the more common ones. In general, 2.5-3 times the maintenance dosage of the inhibitor is
recommended during pretreatment. Cost of the treatment can be reduced by maintaining the
cooling tower at its lowest possible water level to minimize dilution. Discharge restrictions may
also be a limiting factor in selecting a chemical dosage. The report also discusses environmental
aspects of pretreatment (discharge limitations, effects on biox microorganisms, etc.).

Saudi Aramco DeskTop Standards 12