PETROLEUM SEMINAR SCALE

PRECIPITATION

CONTENTS
subject Page. No
List of figures 2
Introduction 3
Scale definition 3
Causes Of Scale 4

Identifying Scale 5
What damage does scale cause ? 9
What are the economics of scale ? 9
Scale Types 10
Identifying Scale Type 19
laboratory identification 19
Scale prevention 20
Scale Inhibitors 21
Scale Removal 22

Reference 24

LIST OF FIGURES

1
 PETROLEUM SEMINAR SCALE
PRECIPITATION

FIG .NO DESCRIPTION PAGE.NO

1 Scale In Tubing 3
2 Scale Deposition In Tubing 6
3 Scale In Near-Well Bore Matrix 7
4 Scale In Injector Wells 8
5 The Relation Between Temperature And Solubility 12
Of (Caco3).
6 The Relation Between Temperature And Solubility 13
Of (Caso4).
7 The Scale Caused By Calcium Sulphate 14
8 The Ionic Strength And (Baso4) Concentration 16
Relationship.
9 The Asphaltene Participation 18

INTRODUCTION
2
PETROLEUM SEMINAR SCALE
PRECIPITATION

Mineral scale formation and deposition on downhole and

surface equipment is a major source of cost and reduce production
to the oil industry.

Fig(1) shows the scale in tubing

Solid scale formation mainly results from changes in physical-

chemical properties of fluids during production or from chemical
incompatibility between injected and formation waters.

SCALE DEFINITION
Scale is a solid mineral deposit usually formed from produced
salt water. Because water constantly dissolves and deposits solids,
scale is an endless problem in the petroleum industry. Scale occurs
in primary production wells, secondary wells, injection wells,
disposal wells, and pipelines that connect well to tank batteries.

3
PETROLEUM SEMINAR SCALE
PRECIPITATION

Wherever water production occurs, a potential for scale

formation exists.

CAUSES OF SCALE
Scale can be caused by any one or a combination of several factors:

1- Pressure changes
2- Temperature changes
3- Iimpurise
4- Additives
5- Variation of flow rates
6- Changes in PH
7- Fluid expansion
8- Gas evaporation
9- Mixing of incompatible water

Mixing of incompatible waters causes the minerals in solution

to form an insoluble precipitate. The precipitate deposits in the
wellbore or the well pump. Scale can develop almost immediately,
or it can build up over several months before becoming noticeable.
Some scale, such as calcium carbonate, develops quickly but is
relatively easy to treat. On the other hand, barium sulfate is
typically slower to form, but it is more difficult to treat.

Once scale has precipitated in the reservoir it reduces the

porosity and permeability. Scale in the reservoir occurs close to the

4
PETROLEUM SEMINAR SCALE
PRECIPITATION

well and the permeability reductions caused by scale is manifested

in an increasing skin.

IDENTIFYING SCALE
Identifying the location and composition of the scale deposit is
the first step in designing a cost effective remediation program.

During injection or production inorganic or organic Products such

as wax and asphalting may be deposited in different parts of the
well or the formation near the wellbore precipitation occurs.

1)PRODUCTION TUBING AND SURFACE EQUIPMENT

Scale in production tubing may occur as a thick layer adhering

to the inside of the tubing. It is often centimeters thick and has
crystals up to 1cm or larger. The primary effect of scale growth on
tubing is to lower the production rate and tubing performance by
reducing the tubing ID and increasing the surface roughness of the
pipe and reducing the flowing area .However the skin is not
affected.

Tubing scale varies in chemical composition, being composed of

layers of scale deposited during the well's history. Often, scales
include asphalting or wax layers, and the layers of scale that are
closest to the tubing may contain iron sulfides, carbonates or
corrosion products. the location of scale deposits in tubing can vary

5
PETROLEUM SEMINAR SCALE
PRECIPITATION

from downhole perforations to the surface where it constrains

production. Scale is often layered and sometimes covered with a
waxy or asphaltene coating.

Fig(2) shows scale deposition in tubing

In surface flow lines and facilities –problematical but not of

such great concern since surface facilities can be more easily
cleared / replaced.

2)NEAR-WELLBORE MATRIX

The carbonate or sulphate scale that is typical of the near-

wellbore region has a finer particle size than tubing scale, on the
order of microns rather than centimetres. It blocks gravel packs and

6
PETROLEUM SEMINAR SCALE
PRECIPITATION

screens as well as matrix pores .ln the formation surrounding the

wellbore and in the Perforations reducing the productivity by
increasing the Pressure losses in the near - wellbore region. Near-
wellbore scale commonly forms after long periods of well shut-in
because cross flow mixes incompatible waters from different
layers. Such scale is thought of as skin removal by chemical
dissolvers or acids can increase production rates dramatically.

Fig(3) shows the scale in near-well bore matrix

3)INJECTOR WELLS

Scale damage to injection well is usually caused by

temperature-activated auto scaling of the injection water. In
addition, incompatible mixing can occur in the near wellbore

7
PETROLEUM SEMINAR SCALE
PRECIPITATION

when injection water contacts either natural formation water or

completion brine. This problem is limited to the early stages of
injection, when injection water is contacting incompatible water
in the near-wellbore region. Scale formed here can decrease the
permeability of the formation and reduce the effectiveness of the
water flood strategy.

Fig (4) shows the scale in injector wells

8
PETROLEUM SEMINAR SCALE
PRECIPITATION

WHAT DAMAGE DOES SCALE CAUSE?

The effect these scales have on a well depends largely on their
location and the amount deposited in the system. Scale can restrict
and completely choke production in the tubing, in the flow lines, at
the sand face, or in the perforations .Scale can deposit in fractures
and formation that are distant from the well bore.

WHAT ARE THE ECONOMICS OF SCALE?

The deposition of inorganic scale in producing wells is a costly
problem in the oil industry. Stuck downhole pump, plugged
perforation and tubing strings, choked flow lines, frozen valves,
equipment damage, and down time during maintenance all
contribute to cost. Scale restricts production and causes
inefficiency and failure of production equipment. As fields mature
and require water flood operation, the scale problems have an
increased effect on well economics.

Scale disposal can be quite costly. The most economical way to

manage wells that tend to scale is to use an inhibitor to prevent the
scale from forming. The savings are even more significant when

9
PETROLEUM SEMINAR
PRECIPITATION

scale prevention
treatments.

SCALE TYPES

1)INORGANIC SCALES
treatment is combined with
SCALE

o
I
i
n
a
g
r
O
s
p
y
T
e
l
a
c
S
stimulation

Many mineral scales are found in the oil field, but calcium
carbonate, calcium sulfate, and barium sulfate are most common
and cause the most concern. Strontium sulfate is less common but
also causes problems. Iron compounds from corrosion and
oxidation are also common.

1.1)CALCIUM CARBONATE
Calcium carbonate or calcite scale is frequently encountered in
oilfield operations. But the calcite has the greatest stability in

10
PETROLEUM SEMINAR SCALE
PRECIPITATION

oilfield circumstances, so it is the most common form of calcium

carbonate encountered in oilfield production operation.

In oil wells, one of the major causes of calcium carbonate

deposition is pressure drop. Calcium carbonate does not exist in
solution as calcium and carbonate ions but as calcium ions and
bicarbonate ions. The precipitation of calcium carbonate can be
expressed by the equation:

2HCO3- + Ca++ CO2 + H2O + Ca CO3

Oilfield problems with calcium carbonate (CaCO3) often centre

around its inverse solubility behavior. Calcium carbonate becomes
less soluble at higher temperature .

The effect becomes more complicated when other precipitation

factors are encountered. In general, the following physical changes
which cause calcium carbonate scale to form:

a- Pressure decrease.

b- Temperature increase.

c- PH increase (such as the loss of CO2)

d- Calcium concentration increase.

e- Carbonate increase.

f- Flashing (in heat treaters).

11
PETROLEUM SEMINAR SCALE
PRECIPITATION

Small changes in temperature can result in large quantities of

calcium carbonate precipitation. Temperature cycling often causes
calcium carbonate or dolomite scaling in heat treaters and the
connecting pipe –just as it dose in home water heaters.

Fig(5) shows the relation between temperature and solubility of

(caco3)

Fortunately, CaCO3 scale can be removed By hydrochloric ( Hcl )

or acetic acid or even with EDTA Chelating chemicals.

1.2CALCIUM SULPHATE
Calcium sulphate deposits in oil fields can exist as Gypsum
(CaSO4 .2H2O) or Anhydrite (CaSO4). Of the two, Gypsum scales
are the most common. The precipitation of calcium sulphate from
water can be expressed as:

12
PETROLEUM SEMINAR SCALE
PRECIPITATION

Ca++ + SO4-- CaSO4

The solubility of calcium sulphate (CaSO4), increases from

ambient to 92F˚ and then decreases at higher temperatures, this
bell-shaped solubility behavior causes problem in wells with
moderate bottom hole static temperatures(100F˚ to 140F˚).

Formation water becomes saturated in calcium sulfate at

bottom hole conditions. As the fluid is produced, its temperature
and pressure decrease, and gypsum precipitates in the wellbore or
wellhead.

Fig(6)
shows the relation between temperature and solubility of (caso4)

Factors which can change the solubility of calcium sulfate in

water and lead to scale deposition are:

- Temperature below 75F˚ and above140F˚

- Decrease in pressure

13
PETROLEUM SEMINAR SCALE
PRECIPITATION

- Increase in calcium or sulfate concentration by admixture with

a second fluid

- Lowering of sodium chloride content (by dilution)

Fig(7) shows the scale caused by calcium Sulphate

Mixing of two waters, one containing a high calcium ion

concentration and the other containing a high sulfate ion
concentration can cause gyp scaling. When such waters are mixed,
the solubility product of calcium sulfate is exceeded and
precipitation occurs until the limit of calcium sulfate solubility is
reached.

14
PETROLEUM SEMINAR SCALE
PRECIPITATION

1.3)BARIUM SULFATE
Barium sulfate (BaSO4) is a highly insoluble substance
(solubility of 2mg/l in water), and it usually cannot be
economically dissolved by a chemical agent. in most cases, the
only way to remove precipitated barium sulfate is by mechanical
scraping or reaming, which is troublesome and costly. Therefore,
managing barium sulfate wells economically requires preventing
precipitation with an appropriate scale inhibitor.

Ba+ + + SO4- - BaSO4 (Solubility 2.0 mg/L)

Factors for BaSO4 precipitation include the following:

a- lower temperature.
b-dilution of brine content.
c- dilution of carbonate content.
d-mixing of incompatible waters.
The commingling of producing zones is the leading cause of
barium sulfate scale problems in the oil field. Because barium
sulfate is more soluble at higher temperature and pressure, it is
routinely encountered in waters from the deeper and hotter
petroleum wells. Water produced from deep, hot wells also tends to
have elevated brine and carbonate content, both of which increase
the solubility of barium sulfate.

15
PETROLEUM SEMINAR SCALE
PRECIPITATION

Fig(8) shows the ionic strength and (Baso4) concentration

relationship
As deep well fluids are produced, the subsequent drop in
temperature and pressure results in the precipitation of barium
sulfate. Produced brine fluids typically are injected as a means of
disposal. Often the brines are mixed with waters from other zones.
If this water is fresh, the reduced salinity of the mixed water
reduces BaSO4 solubility, and scale forms.

2) ORGANIC SCALES

Organic deposits are heavy hydrocarbons (Paraffins or

Asphaltenes) that precipitate as the pressure or temperature is
reduced.

Paraffin deposits in the field are usually considered to be those

that are insoluble in crude oil at producing conditions. They consist

16
PETROLEUM SEMINAR SCALE
PRECIPITATION

of complex mixtures ranging from straight-chain hydrocarbons, the

primary constituent of paraffin waxes, to no paraffin asphaltic
structure, such as asphaltenes. The nature of the precipitated
materials accounts for many of the variations in physical properties
of crude oils.

2.1)WAX PRECIPITATION

Wax deposition occurs primarily due to a drop in temperature

and is most pronounced in tubing, flowlines and surface facilities.
Precipitation of wax can however occur in the formation close to
production wells where gas breakout and expansion causes a drop
in temperature.

Wax deposition in the formation is rare and prevention is not

normally possible. It could be removed at intervals by injecting
aromatic solvents. Heating the solvent can help clear wax out o f
the tubing, but by the time it reaches the bottom of the well, the
temperature has usually equilibrated with the surrounding
formation. Although wax may not form in the formation, it can be
carried into perforations by treatment designed to remove wax
from the tubing, or indeed kill fluids, acid and anything else
bullheaded into the formation.

2.2)ASPHALTENE PRECIPITATION

17
PETROLEUM SEMINAR SCALE
PRECIPITATION

Asphaltenes are high molecular weight substances held in the

oil by various polar compounds. They tend to precipitate out o f the
crude oil at pressures close to the bubble point. They are specific to
oil-type. The problem does not exist in all crudes. The deposition
of asphaltene in the formation and the tubing can have a serious
effect on well productivity. They are insoluble in non-aromatic
solvents and their precipitation cannot easily be inhibited with
chemicals. They can be removed slowly with various aromatic
solvents. Various asphaltene inhibitors are being developed and
should be commercially available in the near future.

Fig(9) shows the Asphaltene participation

18
PETROLEUM SEMINAR SCALE
PRECIPITATION

IDENTIFYING SCALE TYPE

Scale types can be divided roughly into three classes:

1- Water-soluble.

2- Acid-soluble.

3- Acid-insoluble.

This classification is simplified. Scale is seldom deposited in

its pure form. Usually the scale deposit is a mixture of one or more
of the major inorganic components plus corrosion products,
congealed oil, formation fines, paraffin, and other impurities.
However, simple classification is adequate for field analysis.

LABORATORY IDENTIFICATION
Before trying to solve a scale problem, accurately determine
the material deposited. Two methods are used in the laboratory to
identify scales. the instrumental method and a chemical method.

X-RAY diffraction is the instrumental method used most. It is

the fastest laboratory method available and requires the least
amount of sample.

19
PETROLEUM SEMINAR SCALE
PRECIPITATION

In the chemical method, the scale sample is decomposed and

dissolved in chemical solution. The compounds contained in the
scale sample are then analyzed by standard techniques of titration
or precipitation.

SCALE PREVENTION
Prevention is better than cure is particularly relevant to
inorganic scaling in the oilfield environment. At the forefront of
prevention are scale inhibitors chemicals. Scale inhibitors function
by interfering with scale crystal growth.

There are three operational preventions as the following:

1) AVOID MIXING INCOMPATIBLE WATERS

One of the primary causes of scale formation is mixing of two or

more waters which are incompatible. This was illustrated earlier
for the formation of barium sulfate.

2)MODIFY THE WATER AND PH CONTROL:

Scale formation can be prevented by treating the water with
chemicals to remove the undesirable dissolved solids. An example
is the softening of water by the lime and soda ash process to
remove ions that cause calcium carbonate and calcium sulfate
scales. Such procedure may be satisfactory for treating small
volumes of water but may be too expensive for use where large
volumes are treated.

20
PETROLEUM SEMINAR SCALE
PRECIPITATION

Lowering the pH will increase the solubility of carbonate scales

(but may cause corrosion problems). This method is not widely
used in the oilfield, since accurate pH control is needed.

3)CHEMICAL SCALE INHIBITORS

The addition of chemical scale inhibitors prevent scale
deposition by trying up ions that cause scale in solutions.

Chemicals that accomplish this are referred to as sequestering,

chelating and nucleating agents.

STEPS TO BE TAKEN IN SOLVING SCALE PROBLEM ARE:

1- Identify the scale and the reason for its deposition.

2- Remove deposit by chemical or mechanical means.

3- In perforated completion, it may be more satisfactory to

bypass scaled perforations by reperforating.

4- Inhibit against further scale deposition.

SCALE INHIBITORS
Numerous chemical additives are effective at preventing scale
precipitation. Several inhibition products are presented in this
section according to their chemical category:

a- Polyphosphates and Phosphate Esters.

21
PETROLEUM SEMINAR SCALE
PRECIPITATION

b- Slowly soluble Polyphosphates.

1. Propionates.
2. Polyacrylic acid and other Carboxylic acid-containing
Polymers.

CHOOSING AN INHIBITOR

The specific conditions determine inhibitor choice. Always test

inhibitors under the existing conditions. To provide the most
economical treatment for a problem, consider a variety of chemical
scale inhibitors. After you have identified the scale and determined
the well conditions, select the best inhibitor to prevent and control
the problem.

SCALE INHIBITOR EVALUATION

To be suitable for scale inhibition, an inhibitor must:

1- Inhibit scale formation at low concentration.

2- Be stable at reservoir conditions.

3- Be compatible with injection and formation waters/and all

type of chemical used in oilfield.

4- Have a reasonable solubility at reservoir conditions.

5- Be measurable quantitatively at low concentration.

22
PETROLEUM SEMINAR SCALE
PRECIPITATION

6- Have low toxicity and high biodegradability.

7- Have low cost.

SCALE REMOVAL
The best method of removal is one designed around a chemical
analysis of deposit. The chemical composition of scale deposits
can be one or more of numerous possible combinations. This
deposit consisted largely of calcium carbonate but was found to
contain several other constituents.

Some scales are chemically inert to any chemical treatment and

will require mechanical methods of removal. Chemically reactive
scales may be classified as: (1)-water soluble, (2)-acid soluble,
(3)-soluble in chemicals other than water or acids.

1) MECHANICAL METHODS

2) CHEMICAL METHODS

23
PETROLEUM SEMINAR SCALE
PRECIPITATION

REFERENCE
1. Mike Crabtree, David Eslinger, Phil Fletcher, Ashley
Johnson and George King.: "Fighting Scale-Removal and
Prevention". Autumn 1999.
2. M.M.Jordan, G.M.Graham, K.S.Sorbie, A.Matharu,
R.Tomlins and J.Bunney.: "Scale Dissolver Application",
paper SPE 66565, presented at the 1998 formation damage
control conference, Louisiana, 18-19 February.
3. K.U.Raju, J.D.Lynn, W.N.AL-Nasser, M.Ayub and J.Hsu.:
"Low Scaling Potential Horizontal Wells and Scale
Inhibitor Treatment Strategy", paper SPE 50775, presented
for presentation at the 1999 SPE international symposium
on oil field chemistry, Texas, 16-19 February.
4. Collins, R. I. (2005). Predicting the Location of Barium
Sulfate Scale Formation in Production Systems. The SPE
International Symposium on Oilfield Scale. May 11 – 12.
Aberdeen, UK: SPE 94366, 1 – 6.

24