ENGINEERING ENCYCLOPEDIA

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SCALE REMOVAL REVIEW

OF CHEMICAL AND PHYSICAL
TREATMENT METHODS

NOTE: THE SOURCE OF THE TECHNICAL MATERIAL IN THIS VOLUME IS THE PROFESSIONAL
ENGINEERING DEVELOPMENT PROGRAM (PEDP) OF ENGINEERING SERVICES.

WARNING. THE MATERIALS CONTAINED IN THIS MANUAL WERE DEVELOPED FOR THE SAUDI
ARABIAN OIL COMPANY (SAUDI ARAMCO) AND ARE INTENDED FOR THE EXCLUSIVE USE OF
SAUDI ARAMCO EMPLOYEES. ANY MATERIAL CONTAINED IN THIS MANUAL WHICH IS NOT
ALREADY IN THE PUBLIC DOMAIN MAY NOT BE COPIED, REPRODUCED, SOLD, GIVEN, OR
DISCLOSED TO THIRD PARTIES, OR OTHERWISE USED, IN WHOLE OR IN PART, WITHOUT THE
PRIOR WRITTEN PERMISSION OF VICE PRESIDENT, ENGINEERING SERVICES, SAUDI
ARAMCO.
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CONTENTS PAGES

INTRODUCTION................................................................................................... 1
ACIDIZATION....................................................................................................... 2
Example 1.................................................................................................... 3
Solution ....................................................................................................... 3
Example 2.................................................................................................... 4
Solution ....................................................................................................... 4
CHELATION..........................................................................................................6
Example 3.................................................................................................... 6
Solution ....................................................................................................... 6
SCALE CONVERSION .......................................................................................11
SCRAPERS...........................................................................................................15
HIGH PRESSURE JETTING...............................................................................17
GLOSSARY ......................................................................................................... 18

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INTRODUCTION
If equipment is scaled to the extent that its function is impaired, the scale must be removed or
the equipment must be replaced. A multitude of methods are available for removing scale
from equipment including

• Acidizing
• Solvents
• Scraping
• Boring
• Sand blasting
• Jet blasting

A number of ingenious devices have been developed and used to remove scale. Generally,
removing scale is more economical than replacing equipment, especially if the scale is
calcium carbonate. Some scales, CaSO4 and BaSO4, are so hard and tenacious that
explosives have been used to remove them.

The decision to clean or replace equipment requires a thorough knowledge of the processes
that are available to remove scale. Not all processes are available to a given location so
ingenuity must often be used. This module will provide you with some assistance in keeping
production equipment at peak operating efficiency.

Question – Which scale compounds are acid soluble?

Answer – Calcium carbonate.
Question – How can you determine what the effects of acid on a scale will be?
Answer – Try it on a sample of scale.

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ACIDIZATION

Acidizing is the most common chemical method used in the petroleum production industry
for removing scale and for stimulating oil wells. Acids are used to remove scales containing
CaCO3, FeS, Fe2O3, and Fe3O4. Technical grade, 15% hydrochloric acid, also called
muriatic acid, is the preferred acid because of its capacity for dissolving scale, low cost, and
availability. It attacks steel very readily so a corrosion inhibitor must be added to prevent
destruction of steel equipment.

CaCO3 is the only common water-deposited scale that is soluble in acids. It dissolves in acids
very rapidly with the liberation of carbon dioxide:

CaCO3 + 2HCl → CaCl2 + CO2 + H2O

Although HCl is preferred for dissolving CaCO3, many acids will do the job including the
weakest acids as shown in Figure 1.

Acid Concentration CaCO3 CO2 Formed Ca Salt Formed

(%) Dissolved (Std. ft3/gal) (lb/gal)
(lb/gal)
Hydrochloric 15 1.84 6.99 2.04
Acetic 15 1.08 4.09 1.71
Formic 15 1.42 5.38 1.84
Hydrochloric 20 2.50 9.47 2.75
Acetic 20 1.43 5.41 2.25
Formic 20 1.90 7.20 2.47
Hydrochloric 25 3.22 12.20 3.57
Acetic 25 1.80 6.82 2.84
Formic 25 2.40 9.09 3.12

FIGURE 1. Capacities of Some Acids for Dissolving CaCO3

Acids other than HCl are generally not used for dissolving CaCO3 because they cost more and
are less available. Sulfuric acid, phosphoric, and sulfamic acids are not used because they
form sulfate ion that can reprecipitate calcium ions as CaSO4:
CaCO3 + H2SO4 → CaSO4 + CO2 + H2O
The amount of hydrochloric acid required to dissolve a given amount of CaCO3 can be
readily calculated from the equation for the reaction given above.

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Example 1
How many pounds of hydrochloric acid are required to dissolve 145 pounds of CaCO3 scale?

Note: Calculate the number of pounds of HCl as if it were a pure compound. In the next exercise,
we’ll calculate how many gallons of 15% HCl are needed.

Solution
Step 1. The molecular weight of CaCO3 is 100.09 and of HCl is 36.46. So from the
equation

CaCO3 + 2HCl → CaCl2 + CO2 + H2O

100.09 pounds of CaCO3 reacts with 2(36.46) or 72.92 pounds of HCl.

Step 2. Therefore, 145 pounds of CaCO3 requires:

(72.92) (145)
= 105.64 pounds of HCl
100.09

The pounds of HCl present in a gallon of HCl solution of a given concentration can be
obtained from a correlation of the concentration with specific gravity. Figure2 gives the
amount of HCl in a gallon of HCl solution of various percentage compositions.

Concentration Specific HCl

HCl (%) Gravity (lb/gal)
5 1.0230 0.4273
10 1.0474 0.8741
15 1.0726 1.343
20 1.0980 1.833
25 1.1238 2.346
30 1.1492 2.877
FIGURE 2. Concentration and Specific Gravities of HCl Solutions

Sometimes, the specific gravity of HCl solutions is expressed in degrees Baumé (° Bé). These
can be converted to specific gravity by the formula.

145
degrees Baumé = 145 –
sp. grav.

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Example 2
How many gallons of 15% HCl, specific gravity 1.0726, are required to dissolve 145pounds
of CaCO3?

Solution
Step 1. From the preceding exercise, we needed 105.64 pounds of HCl to dissolve 145
pounds of CaCO3. Calculate how many gallons of 15% HCl are required to contain
105.64 pounds of HCl.

Step 2. From the table in Figure 2, 15% acid contains 1.343 pounds of HCl per gallon of
solution:

105.64
gallons required = = 78.66 gallons 15% HCl
1.343

145
one gallon dissolves = 1.84 pounds of CaCO3
78.66

It is a good idea to check the specific gravity of HCl when it is delivered to ensure that the
concentration is to specifications. The per cent of HCl in the solution can be estimated from
its specific gravity by subtracting and multiplying by 200 (Figure 3).

% HCl = 200(sp. grav. -

1.000)

If specific gravity is 1.0980:

% HCl = 200(1.0980 -
1.000)

= 19.6%

[Actually, it is 20% but 19.6% is close.]

FIGURE 3. Estimating the Concentration of HCl from Specific Gravity

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In actual practice, the volume of CaCO3 to be dissolved is estimated from its thickness as
determined by X-rays, calipers, or other methods. The amount of HCl required to dissolve the
total amount of CaCO3 is then acquired. By dry weight, a cubic foot of CaCO3 contains about
175 lbs of CaCO3. Since one gallon of 15% HCl dissolves 1.843 lbs of CaCO3, then a cubic
foot of CaCO3 will require 175/1.843, or, 95 gallons of 15% HCl.

By these methods, a table giving the dissolving capacity of various concentrations of HCl to
dissolve CaCO3 can be made (Figure 4).

Concentration CaCO3 Acid to CO2 Formed

(%HCl) Dissolved Dissolve CaCO3 (std. ft3/gal)
(lb/gal) (gal/ft3)
5. 0.586 299. 2.221
7.5 0.890 197 3.367
10. 1.201 146. 4.551
15. 1.844 95. 6.991
28. 3.659 48. 13.850

FIGURE 4. Capacity of HCl to Dissolve CaCO3

The reaction of CaCO3 with HCl is very fast if the CaCO3 is clean. If it is oil coated, the
reaction is very slow. If the oil coating is heavy, a solvent rinse might be required to remove
the oil prior to acidizing. A light contamination by oil is usually overcome by including a
surfactant in the acid. The volume of CO2 liberated by acidizing, as illustrated in the
preceding exercise, can be very large and it can be generated rapidly. Provision should be
made to vent the CO2 formed to prevent excessive pressures and unexpected contaminations.

Even though corrosion-inhibited acid is used for scale removal, some corrosion does occur.
For this reason, an acid treatment should be followed by a water rinse and a neutralizing rinse
with a 3% solution of soda ash.

The corrosion inhibitor used in 15% HCl usually protects steel best of all. The inhibitor might
not be very effective in preventing attack of stainless steel. Corrosion tests should be done or
such data requested from the supplier of the inhibitor to insure that stainless steel will not be
damaged. Acids other than HCl are preferred for stainless steel. Corrosion of stainless steel
is very low in hydroxyacetic (glycolic) acid. Stainless steels are practically inert to
hydroxyacetic acid containing 500 ppm of Fe++. Even inhibited acid will remove
galvanizing (zinc). Galvanized equipment should not be acidized.

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CHELATION

Chelating agents are compounds that form water-soluble complex ions with simple cations.
Some chelant complexes are so stable that they can dissolve scale compounds and can
prevent precipitation of scale-forming cations. Chelants are used to clean boilers, soften
water, and remove scale. Because of their high cost ($1/lb and up), they are used to a limited
extent at present. Chelants present distinct advantages in some problems of scale removal,
and their cost is declining.

If C represents a chelant, M++ represents a cation and MC++ the complexed cation, then the
chelation equilibrium can be written as shown in Figure 5. Note that the higher thestability
constant, the greater is the complexation, or chelation, of the cation. The resulting effect of
adding a chelating agent to a solution of scale-forming cations is to lower the effective
concentration of the cations. If CaSO4 is dissolved in water, the resulting solution is saturated
with Ca++ and SO4-- ions. By adding a chelant, the Ca++ ions are complexed so that the
solution is able to dissolve a greater amount of CaSO4 before it becomes saturated.

C + M++ ↔ MC++

MC++
KS =
C M++

Where Ks is the stability constant

FIGURE 5. Expression for the Stability Constant

Example 3
This example illustrates the application of chelating agents in terms of how much chelating
agent is required and the cost.

1. Ten grams of CaCO3 is stirred in 1 liter of 0.5 M EDTA solution. Will it all dissolve?

Solution
Step 1. The solubility product constant (Ksp) for CaCO3 is 0.87 × 10-8 and the stability
constant (Ks) of EDTA for complexing Ca++ is 3.89 × 1010.

Ksp = [Ca++][CO3--]

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Step 2. The molecular weight of CaCO3 is 100.08. Therefore, 10 g is 0.1 M. If the EDTA
dissolves all the CaCO3, then the CO3-- concentration will be 0.1 M. Almost all of
the Ca++ will be complexed by the EDTA.

0.87 × 10-8 = [Ca++](0.1)

[Ca++] = 0.87 × 10-7

Step 3 If all the CaCO3 is to dissolve, the uncomplexed Ca++ concentration has to be less
than 0.87 × 10-7.

[CaEDTA]
Ks =
[EDTA] [Ca++]

Step 4. If the CaCO3 saturates the EDTA solution, the right side of the equation will be
greater than Ks. If the EDTA solution dissolves all the CaCO3, then Ks will be
larger than the right side of the equation.

[Ca++] = 0.87 × 10-7

CaEDTA + EDTA = 0.5

and

CaEDTA = 0.1 – Ca++

Substituting

0.1 – [Ca++]
Ks =
(0.5 – 0.1 + [Ca++]) [Ca++]

3.89 × 1010 > 2.87 × 106

Therefore, all 10 grams will dissolve.

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2. How many grams of CaCO3 will 1 liter of 0.5 M EDTA dissolve?

Step 1. If [Ca++] is of the order of 10-7, then the ratio of [CaEDTA] to [EDTA] is very
large, about 103. Therefore, when the EDTA is saturated with Ca++, essentially all
the EDTA is in the CaEDTA complex. It will dissolve CaCO3 nearly on a
stoichiometric ratio.

CaCO3 + EDTA ↔ CaEDTA++ + CO--

3

Step 2. So, 1 mole of EDTA dissolves nearly one mole of CaCO3. We have 0.5 M of
EDTA, so it will dissolve 0.5 M of CaCO3.

Molecular weight of CaCO3 = 100.8

0.5 M = 50.4 g

Therefore, 50.4 grams of CaCO3 will dissolve in 1 liter of 0.5 M EDTA.

One liter of 0.5 M EDTA contains 146 grams or about 0.322 pounds. At $1 per pound, the
cost of the EDTA would be $.32 or approximately 10 times the cost of acidization.

Some common complexing agents are described in Figure 6. Ethylene-diamine-tetra-acetic

acid (EDTA) is not very soluble in water alone but is very soluble in NaOH or KOH
solutions. It can be purchased as the sodium salt (Na4EDTA) and dissolved directly, but the
acid form is less expensive. Note from Figure 20 that the molecular weight of most of the
chelating agents is very high, which contributes to their cost. For example, one Mole of
EDTA (Mol. wt. 292.2) complexes one mole of Ca++ (at. wt. 40.08). Therefore, it requires
7.3 ppm of EDTA to complex 1 ppm of Ca++. NTA, which has a lower molecular weight
than EDTA, will dissolve about 350 mg of CaCO3 per gram of NTA.

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FIGURE 6. Some Common Chelating Agents

Although chelants will dissolve CaCO3, they cannot compete with HCl, which is much
cheaper. For CaCO3, they are used only in preventing the formation of CaCO3, such as in
boiler water. Chelants have more utility in dissolving scales of CaSO4, SrSO4, and BaSO4,
which are not soluble in acids.

Chelants are used successfully to dissolve both gypsum (CaSO4 • 2H2O) and anhydrite
(CaSO4). Spent EDTA can be regenerated by neutralizing the chelate solution with acid,
which causes the Ca++ to be released and reprecipitated as CaSO4. The clarified solution is
then made alkaline again with NaOH or KOH (Figure 7).

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CaEDTA + H2SO4 → CaSO4 + H2EDTA

H2EDTA + 2 NaOH → Na2EDTA + 2H2O

FIGURE 7. Regeneration of Spent EDTA

Glycolic acid (see Figure 6) is also useful in disintegrating hard deposits of gypsum (Figure
8).

Chelant CaSO4 • 2H2O Removed

(%)
13% Na4EDTA 30-90
? Na3NTA 88
40% Potassium glycolate 100
40% Sodium glycolate 20-30

FIGURE 8. Effect of Some Chelants in Removing Gypsum

Even though chelants are able to remove CaSO4, they are not widely used for the purpose.
The “converters”, described later in this module, cost less and are the preferred treatment for
CaSO4 scales.

BaSO4 is very difficult to remove chemically, and one must usually resort to mechanical
removal. Proprietary solvents for BaSO4 are being promoted on the North Sea. Heretofore,
these consisted of concentrated solutions of EDTA or DTPA with potassium hydroxide
(KOH). These solutions will dissolve about 25 grams of BaSO4 per liter, but the action is
very slow. A typical treatment requires 72 hours contact time with the circulating solvent.
Newer formulations have been developed that are much faster and have higher capacities for
BaSO4 and CaSO4. It is expected that these newer formulations will have wide applications
in the future.

There has been little reported work on the use of chelants in removing SrSO4 scales.
However, the stability constants for Sr++ complexes are of the same order of magnitude as
Ba++, so it is anticipated that the newly-developed solvents for BaSO4 will also work for
SrSO4.

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SCALE CONVERSION
Scale converters are chemical agents that convert a scale to another chemical form that can
be removed. Conversion agents find their greatest use in removing CaSO4 scales.

Inorganic converters are alkaline solutions, usually carbonates or hydroxides, that react with
CaSO4 and convert it to acid soluble CaCO3 or Ca(OH)2. One converting agent is illustrated
by the reaction of ammonium carbonate (Figure 9).

CaSO4 + (NH4)2CO3 → CaCO3 + 2NH4+ + SO4- -

CaCO3 + 2HCl → Ca++ + CO2↑ + 2Cl- + H2O

FIGURE 9. Action of a Converting Agent on CaSO4

Removal of CaSO4 with a converting agent is a two-step process. Treatment with the
converting agent is a slow process requiring about 24 hours “soaking” time. The subsequent
acid step is very fast, however. In stimulating CaSO4-choked wells or in cleaning out
perforations, the CaSO4 is usually oil-soaked. In these cases, the conversion/removal process
can be quite complex, as illustrated by the procedure for a West Texas well (Figure 10). The
purpose of the initial treatment with organic scale converter is to soften the CaSO4 so it is
more completely reacted by the inorganic converting agent, which follows in a subsequent
step.

1. Run bit to T.D. to clean out hole. If open hole, run jet wash tool.
2. Pump four drums of paraffin solvent.
3. Shut in for 24 hours.
4. Flow or swab back load and residue to pit.
5. Pump two drums organic scale converter diluted 1:1 with fresh water.
6. Shut in for 24 hours.
7. Flow or swab back load and residue to pit.
8. Pump 1,000 gallons of 28% HCl.
9. After 15 minutes, flow or swab back load and residue to pit.
10. Pump 1,500 gallons inorganic scale converter.
11. Shut in for 24 hours.
12. Flow or swab back load and residue to pit.
13. Stimulate with 4,000 to 8,000 gallons of 28% HCl.
14. Flow or swab back load and residue to pit.
15. Return well to production. Clean up location.

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FIGURE 10. Conventional Scale Converter Treatment Procedure1

1R. C. Hoerauf, “New Two-Step Xylene Scale Treatment Removes Calcium Sulfate”,Oil and Gas J., pp 56-59, Aug. 22,
1988
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Recent improvements in the CaSO4 conversion treatment reportedly reduce the number of
steps required from five steps to two steps. This is accomplished by combining the
oil/paraffin removal agent and the converting agent into one treatment in the form of an
emulsion of xylene and inorganic scale converter solution (Figure11).

1. Run bit to T.D. to clean out hole. If open hole, run jet wash
tool.
2. Pump 1,500 gallons of xylene-scale converter emulsion.
3. Shut in for 24 hours.
4. Flow or swab back load and residue to surface.
5. Stimulate with 4,000 to 8,000 gallons of 28% HCl.
6. Flow or swab back load and residue to pit.
7. Return well to production. Clean up location.

FIGURE 11. Xylene-Scale Converter Stimulation Treatment1

Organic scale inhibitors do not convert CaSO4 to acid-soluble compounds. Rather, they
soften the scale to a sludge-like consistency that can be washed out. Compounds used for this
purpose are potassium glycolate, glycolic (hydroxyacetic) acid, aminomethylene
phosphonates, sodium citrate and potassium acetate. These compounds are weak chelants for
Ca++ and, therefore, dissolve a small amount of CaSO4. Their main purpose is to soften the
scale. This generally requires a soaking time of 24 hours.

A comparison of the rate of disintegration of CaSO4 by an organic converting agent (10%

aminomethylene phosphonate) and an inorganic converting agent (NaOH) is given in Figure
12.

1R. C. Hoerauf, ibid.

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FIGURE 12. Disintegration of Gypsum in Organic and Inorganic Converting Agents

From results in Figure 12, AMP with 15 pounds per barrel (PPB) of KOH appears to be faster
than 30% NaOH. Calcium sulfate deposits vary so much in physical characteristics from
location to location that it is recommended that proposed scale converters be tested on
samples of the actual scale prior to use. All chemical scale removal works faster at higher
temperatures and when agitated by vibration or circulation.

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SCRAPERS

Mechanical scraping is most commonly used on individual joints of pipe or on thin scales in
pipelines. Joints of pipe or tubing are scraped by various types of cutter heads mounted on a
rotating lance with air or fluids assisting in removing the scrapings. Flow-propelled scrapers
are used in pipelines for thin scales. The risk of sticking the scraper is too great for scraping
of thick scales. For scales in pipelines that cannot be removed by acid or other chemicals,
early detection or frequent scraping are the only remedies.

Abrasive scrapers made of polyurethane foam with a rubber or plastic cover are the simplest
type of pipeline scraper. More sophisticated devices use gear-type cutters or wire brushes that
rotate against the pipe wall. Ducts through the scraper allow fluid to wash the cuttings ahead
of the scraper. Wire brushes are self-cleaning since fluid can bypass the scraper through the
brush bristles and carry scrapings ahead of the scraper (Figure 13).

FIGURE 13. Brush Scraper

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A flowline clean out usually consists of several steps (Figure 14).

1. Slug of solvent followed by a ball

2. Slug of inhibited HCl followed by a ball
3. Slug of neutralizing solution, NaOH or Na2CO3

FIGURE 14. Steps in Cleaning a Pipeline

Water gelled with Kelzan XC polymer increases the solids-carrying capacity of the pipeline
fluid when scraping. The amount of scale in a pipeline, even a thin scale, can be enormous.
A 200-mile long 36-inch pipeline coated with 1/8-inch of gypsum contains 3,710 tons of
scale.

Downhole scraping of production tubing is generally not practical. If a scale cannot be

removed by chemicals, the usual recourse is to pull the tubing and clean it on the surface.
Attempts were made to break up CaSO4 deposits downhole with an ultrasonic vibrator that
was capable of emitting power levels of 50 hp. Although successful in some cases, problems
with the ultrasonic blaster were numerous and the device was withdrawn from the market.

Plugged perforations have been cleaned with explosives, but this is not practiced anymore.
Chemicals are used to clean perforations, if applicable, and, if these fail, the casing is
reperforated.

Plugged formation faces offer the same problems as perforations in accessibility. In some
cases, hydraulic fracturing is the only way to stimulate a production well that is plugged with
scale. For open-hole completions, enlarging the hole with an underreamer can restore
plugged formation faces.

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HIGH PRESSURE JETTING

High pressure jetting is always an attractive, and often successful method for cleaning scaled
materials. In this method, high pressure jets of water are impacted against the surface to be
cleaned. Scale is dislodged by the force of the water jet and is swept away by the flow.
Typically, jet devices operate at pressures of 2,000-5,000 psi so the force imparted to the scale
is enormous. Options are to incorporate detergents, solvents, or acids in the jet to facilitate
cleaning. Pulsing would probably increase the effectiveness of the jet but is not practiced.

Jets are attractive for reasons given in Figure 15.

1. Less planning time required

2. Costs less than chemical cleaning
3. Less corrosion damage
4. Fewer disposal problems
5. Effective in multipath systems where some
paths are plugged
6. Low danger of by-product gases
7. Effective for wide range of materials

FIGURE 15. Advantages of High Pressure Jetting

Jet heads for pipelines can be self-propelled. However, their jets must be supplied through
flexible tubing that is dragged or pulled through the pipe (Figure 16). For this reason, the
pipeline must be entered and drained over short intervals. Jets are not as effective through a
column of water so the pipeline must be kept well-drained. Jets probably find their best
applicability to vessels too large to be filled with solvents or to joints of pipe that can be jetted
with a lance.

FIGURE 16. Jetting a Pipeline

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GLOSSARY

ball A compressible sphere of plastic foam or other material

for separating fluids in a pipeline.

chelant A chelating agent.

(to) chelate To form a complex ion by joining a chelating agent to a

metal ion (cation).

complex ion An ion that in composed of more than one chemical

groups such as a chelated metal ion.

conversion agent A compound that reacts with a scale to change its

chemical or physical properties; same as scale converter.

DTPA Abbreviation for diethylene-triamine-penta-acetic acid, a

chelating agent.

EDTA Abbreviation for ethylene-diamine-tetra-acetic acid, a

chelating agent.

glycolic acid Acetic acid with an alcohol group, C2H4O3; same as

hydroxyacetic acid.

hydroxyacetic acid Acetic acid with an alcohol group, C2H4O3; same as

glycolic acid.

muriatic acid Common name for industrial grade hydrochloric acid.

NTA Abbreviation for nitrilotriacetic acid, a chelating agent.

scale converter A compound that reacts with a scale to change its

chemical or physical properties; same as conversion
agent.

(to) sequester To extract or separate such as a chelating agent extracting

Ca++ from CaCO3.

stability constant The concentration of a chelated ion divided by the

product of the concentrations of the unreacted chelating
agent and free metal ion.

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