CHAPTER 3.

10
REFINERY CHEMICAL CLEANING

Chemical cleaning of process equipment is a regular part of a refiner's maintenance and turnaround schedule. Not
only does proper cleaning extend run time, but also it prevents expensive equipment replacements by removing
corrodents, scale, fouling, and other detrimental compounds which can limit the life of the equipment. Benefits of
efficient chemical cleaning are:

 Improved heat transfer

 Longer run times.
 More efficient operations.
Less maintenance and equipment replacements. Reduced utility and energy consumption rates.

Hydrocarbon service cleaning

Heat exchangers are the most commonly cleaned piece of equipment in the refinery. Corrosion and fouling can
greatly reduce heat transfer and increase energy consumption. Plugged tubes and tube warpage, as a result of
insufficient cleaning methods, can also reduce exchanger efficiency.

Heat exchangers are usually unbolted and the tube bundle is removed. The inside shell is inspected for damage or
corrosion and then washed with high pressure water on-steam. The tube bundle may be taken to a steam-heated vat
and immersed in a caustic-dip solution for hydrocarbon removal or degreasing. Residence time in the caustic
solution varies depending on the type and amount of foulant present on the tubes.

Many refiners dip the tube bundle in inhibited HCl steam vats. Iron sulfide, iron oxide, and scale can be easily
removed by this method. Residence times can vary from ½ to 2 hours depending upon the acid strength and
amount of foulant present.

Following caustic and/or acid soaking, tube-side hydrolancers with water jets (5,000 to 10,000 psig) are used to
unplug tubes and remove internal corrodents and foulants.

Detergent spraying and soaking, followed by water rinses is used for all bundles and equipment made of aluminum.
Highly acidic or alkaline-based cleaners are not recommended because of their corrosiveness to this metal.

Stainless steel equipment is usually cleaned with citric, phosphoric, or inhibited sulfamic acids. Various chelants
have been used for cleaning, but are usually very expensive for the refiner.

Alkylation units using hydroflouric acid present special cleaning problems for the refiner. If HCl is used to clean
exchanger bundles, HZS can form and become a serious hazard to workers in the area, Most refiners are using
inhibited HzSO4 to clean tube bundles. Neutralizing with soda ash and purging with ammonia is used before
removing the exchanger tubes from the shell.

Water Side Cleaning

Scale, corrosion, solids buildup, and biological growths can also be a major problem to the refiner for exchanger
and condenser cleaning. Many plants use on-stream cleaning methods by injecting acid, monitoring its
concentration, and recovering it downstream for scale and hardness buildups. Still others use 150 psi steam and
air blowing for cleaning water sides of coolers and condensers. Water service bundles are usually predipped in
special solvents and precoating chemicals to prevent rusting.

Columns and Towers

A hot aromatic solvent wash followed by a hot water and steam rinse is used to loosen iron sulfide deposits in
columns and towers. Trays, weirs, and downcomers can be effectively cleaned with this method.
Heavy oil columns require more extensive cleaning approaches. Superheated steaming followed by hot No. 2 fuel
oil rinses or light cycle oil rinses plus resteaming and water rinsing usually cleans towers in this type of service.
Steaming time should be from 8 to 24 hours because of the heavy products which remain in the tower.

Storage Tanks

Storage tanks can be washed with No. 2 fuel oil followed by a water soluble degreaser and a water wash to remove
deposits and corrodents. Excess paraffin buildups in crude tanks can be removed by using several non-chlorinated
solvents.

Decoking Crude Oil Furnaces

Coked furnace tubes are quite common in the refinery. Heat transfer to the tubes is lost and process flow is reduced.
The most common method of decoking is with steam and air.

Steam is injected into each coil of the furnace and the firebox is purged. The furnace is then lit and operated with
the maximum limit of excess air to raise the coil outlets to at least 1000°F.

Compressed air is then injected into each coil and the furnace coil temperatures are monitored by installed
thermocouples. Injection of the compressed air causes combustion of the coke in the furnace tubes and is indicated
by a rise in temperature of the tubes. Air rates are increased to maintain a combustion of the coked tubes until a
maximum temperature of l200°F is reached. The tubes are continuously checked for hot spots.

When combustion is completed and the tube is thoroughly decoked, a substantial drop in thermocouple temperature
will occur. As a further check of decoking, air rates to the tube can be raised and if no temperature increase is
noted, the tube can be assumed to be decoked.

Following decoking, each coil is checked, the compressed air rates are discontinued and fire to the firebox is shut
off. Steam is allowed to remain in the tubes until a cooler temperature of 400°F is reached.

Effluent from the tubes is usually piped to a vent stack and water injection prevents it from discharging to the
atmosphere.

Various alloys for furnace tubes have temperature limitations for decoking. Here is a sample of the most popular
alloys and their maximum temperature limits: carbon steel -l300°F max.; 7 to 9 percent Chrome - 1,400°F
maximum and HK-40 – 1850°F maximum.

Pretreatment

Following exchanger cleaning, exchangers in hydrocarbon services should be pretreated. Pretreatment can be
divided into two categories - internal and external. Internal pretreatment refers to an increased antifoulant dosage
(2 -5x maintenance dosage) for the first 1 - 2 weeks of operation. External pretreatment refers to the establishment
of a protective film of antifoulant prior to commissioning the exchanger. Standard external pretreatment methods
are as follows:

PRETREATMENT METHODS

I. HIGH PRESSURE SPRAY METHOD

A. Equipment Required

1. Hydroblast equipment and crew.

2. Collecting trough (recommended).

3. Transfer pump and hoses (optional).

4. Safety Equipment:
 a. Slicker Suit
b. Gloves
c. Face Shield
d. Rubber Boots
e. Breathing Air Mask (optional)

B. Procedure

1. The bundle is cleaned thoroughly using normal hydroblasting methods, and pitched at a 1O~Z0o
angle to allow excess water to drain. Blow tubes dry with nitrogen or air if possible. Bundle
pretreatment should begin as soon after cleaning as possible.

2. A plywood sheet (or substitute material such as visqueen) is fastened to the lower end of the
bundle to minimize fugitive spray. A trough placed beneath the low end of the bundle to collect
chemical run-off is recommended. The trough may be made by cutting a 55 gallon drum
lengthwise.

3. Antifoulant is transferred to the hydroblast reservoir. A transfer pump is recommended if head

pressure in the bulk tank is insufficient.

4. Each tube is hydroblasted with neat antifoulant at normal hydroblast pressures.

5. Excess chemical is collected in the trough, and may be reused in the hydroblast equipment
depending on the amount of impurities present, whether an emulsion has formed, etc. Only a thin
layer of antifoulant is necessary for successful pretreating, and flows should be adjusted if
possible to minimize run-off of excess chemical.

6. Best results are obtained if the shell side is also sprayed at high pressure. In this case, excess
chemical is not collected.

7. The bundle should be installed immediately after pretreating if possible. If the bundle is to
remain outside of the shell for an extended period, it should be covered to protect it from the
elements.

C. Chemical Inventory for Pretreating - Approximately 25 gallons per bundle.

D. Exposure Factor - 4* See Exposure Factor Index

E. Advantages

1. Best results have been documented with this method.

2. Good contact between chemical and metal is guaranteed.

3. Some degree of additional cleaning is provided.

4. Small chemical inventory is required.

F. Disadvantages

1. flydroblast crew must be supervised.

2. High exposure factor.

II. DIP METHOD

A. Eqizipment Required
 1. A vat large enough to submerge entire bundle.

Z. Transfer pump and hoses.

3. Crane

B. Procedure

1. The bundle is cleaned thoroughly using normal hydroblasting methods and pitched at a 10-20°
angle to allow excess water to drain. Blow tubes dry with nitrogen or air if possible. Bundle
pretreatment should begin as soon after cleaning as possible.

2. The bundle to be pretreated is placed in the vat pitched at a slight angle to prevent air pockets in
the tubes when the antifoulant is added.

3. Antifoulant is transferred from the bulk tank to the vat using a transfer pump if necessary. The
antifoulant may be diluted with a Naphtha or Kerosene distillate. The bundle should be
completely covered with antifoulant for 5-10 minutes.

4. After sufficient contact time is allowed, the bundle is lifted from the vat and pitched to allow
excess antifoulant to drain.

5. Insert bundle into shell. Exchanger should be put in service as soon as is practical.

6. When all bundles have been dipped, unused antifoulant may be stored and reused at a later time.

C. Chemical Inventory for Pretreatment

1. 400-4,000 gallons, depending on bundle size. Actual volume should be calculated.

2. Actual consumption is approximately Z5 gallons per bundle.

D. Exposure Factor – 2 (see Exposure Factor Index)

E. Advantages

1. Low exposure factor.

Z. Documented results have been good.

3. Fastest method.

F. Disadvantages

1. Large chemical inventory to pretreat.

2. Possible chemical contamination.

III PUMP THROUGH METHOD

A. Equipment Required
 1. Pump and hoses. (A hand pump is sufficient)

2. Drains and vents on hot and cold fluid inlets and outlets.

B. Procedure

3. The bundle is cleaned thoroughly using normal hydroblasting methods and pitched at a
10-20° angle to allow excess water to drain. Blow tubes dry with nitrogen or air if
possible. Bundle pretreament should begin as soon as possible.

4. The bundle is inserted into the shell, and the shell heads are installed. If hydrotesting
must be performed, it should be done at this time. After hydrotesting, drain as much water
as possible.

5. Chemical is transferred from the bulk tank or drums to the shell side of the exchanger via
a transfer pump through the shell side drain. The chemical can be used neat, or can be
diluted with a Naphtha or kerosene distillate. If the chemical is diluted, proper mixing
must be assured.

6. Open the shell side vent. A full shell side is indicated by the leakage of antifoulant from
the vent. At this time, pumping is stopped and the exchanger vents and drains are
blocked-in. Allow 5-10 minutes contact time between antifoulant and metal surfaces.

7. If neat chemical is used, the transfer pump is then piped to take suction from the drain of
the shell side of the exchanger, and the discharge is piped to the tubeside drain. Nitrogen
pressure may also be used to transfer the fluid. After transfer, block-in the shell side of the
exchanger to insure that no air enters.

The tube side is filled in the same manner as the shell side, using leakage from the tube
side vent to indicate a full exchanger. Again, 5-10 mintues is allowed for contact time.

The procedure is repeated for additional exchangers. Exchangers should be put in service
within a minimum time frame.

If only one side of the bundle is to be pretreated, the antifoulant (or antifoulant mixture)
may be left in the exchanger and pushed through the unit.

8. If diluted chemical is used, it is recommended that the mixture be allowed to remain in

the exchanger until startup.

C. Chemical Inventory for Pretreatment

9. 200 - 2,000 gallons, depending on bundle size. Actual volume should be calculated from
exchanger specification sheets.

10. Consumption is approximately 25 gallons per bundle.

D. Exposure Factor - *1 (See Exposure Factor Index)

E. Advantages

1. Lowest exposure factor.

2. Minimum equipment requirement.

F. Disadvantages
 1. Large inventory required if neat chemical is used.

2. Drains and vents are necessary.

IV. LOW PRESSURE SPRAY METHOD

A. Equipment Required

1. Pump-up bug sprayer with nozzle extension.

2. Collecting trough (recommended)

B. Procedure

1. The bundle is cleaned thoroughly using normal hydroblasting methods and pitched at a 10-Z0 0
angle to allow excess water to drain. Blow tubes dry with nitrogen or air if possible. Bundle
pretreatment should begin as soon after cleaning as possible.

2. Chemical is transferred from bulk tank to spray can.

3. With the bundle at a 10-20° pitch, spray each tube. Excess chemical is collected in trough
located below the low end of the bundle and reused in the spray can.

4. Spray the shell side as well as the tube side to obtain best possible
coverage.

C. Chemical Inventory for Pretreatment - Approximately 25 gallons per bundle.

D. Ezposure Factor - 3* (see Exposure Factor Index)

E. Advantages

1. Minimal equipment requirement.

2. Small chemical inventory is necessary.

F. Disadvantages

1. High exposure factor.

2. Filling spray can is repetitive and time consuming.

EXPOSURE FACTOR INDEX

1. Least Exposed Personnel in the area are not
exposed to antifoulant

2. Little Exposure Antifoulant is in a vat open

to the atmosphere. Personnel
in the area could be exposed to
antifoulant.

3. Exposed Antifoulant is sprayed at low

pressure. Some chemical is
vaporized. Personnel in close
proximity are exposed.
 4. Most Exposed Antifoulant is sprayed at
high pressures. High degrees of
vaporization. Personnel in
the area are exposed.

NOTE: The toxicity of antifoulants has been determined. Consult the Material Safety
~
Data Sheets for more detailed information.