SCALE

What is it? Why does it form?

Types of scales:
1) Calcium/Magnesium carbonates - CaCO3 & MgCO3 - formed from the
following occurrences:
a)Change in formation or system temperatures and/or pressures:
As the temperature increases, carbonate scaling tendencies
increase. As pressure decreases, carbonate scaling tendencies
increase.
b)Decrease in solubility due to mixing incompatible waters: If one mixes
two or more waters with a Total Dissolved Solids (TDS) difference of
more than 20%, carbonate scale can occur.

2) Calcium sulfate - CaSO4 - formed from the following occurrences:

a)Change in formation or system temperatures and/or pressures: As the
temperature increases, Calcium sulfate scaling tendencies decrease up
to —118 degrees F then increase from --118 to —136 degrees
F. As pressure decreases, Calcium sulfate scaling tendencies
increase.
b)Decrease in solubility due to mixing incompatible waters: If one mixes
two or more waters with a Total Dissolved Solids (TDS) difference of
more than 20%, Calcium sulfate scale can occur.

3) Barium and Strontium sulfates - BaSO4 and SrSO4 respectively are

formed from the following occurrences:
a)Barium sulfate will generally occur whenever two or more waters are
mixed with one of the water(s) containing greater than 2.0
milligrams per liter (mg/1) Barium and the other water(s) containing
greater than 150-300 mg/I soluble sulfate.
b)Strontium sulfate scales will generally occur based upon either an
increase in water temperature and/or a decrease in water pressure as
well as oversaturation when two different TDS waters are mixed.
 SCALE

What is it? Why does it form?

Types of scales:
1) Calcium/Magnesium carbonates - CaCO3 & MgCO3 - formed from the
following occurrences:
a)Change in formation or system temperatures and/or pressures:
As the temperature increases, carbonate scaling tendencies
increase. As pressure decreases, carbonate scaling tendencies
increase.
b)Decrease in solubility due to mixing incompatible waters: If one
mixes two or more waters with a Total Dissolved Solids (TDS)
difference of more than 20%, carbonate scale can occur.

2) Calcium sulfate - CaSO4 - formed from the following occurrences:

a)Change in formation or system temperatures and/or pressures:
As the temperature increases, Calcium sulfate scaling tendencies
decrease up to —118 degrees F then increase from --118 to —136
degrees F. As pressure decreases, Calcium sulfate scaling tendencies
increase.
b)Decrease in solubility due to mixing incompatible waters: If one
mixes two or more waters with a Total Dissolved Solids (TDS)
difference of more than 20%, Calcium sulfate scale can occur.

3) Barium and Strontium sulfates - BaSO4 and SrSO4 respectively are

formed from the following occurrences:
a)Barium sulfate will generally occur whenever two or more waters are
mixed with one of the water(s) containing greater than 2.0 milligrams
per liter (mg/1) Barium and the other water(s) containing greater
than 150-300 mg/I soluble sulfate.
b)Strontium sulfate scales will generally occur based upon either an
increase in water temperature and/or a decrease in water pressure
as well as oversaturation when two different TDS waters are mixed.
 " THE KIT "

CONTENTS:

1)XYLENE

2)15% HYDROCHLORIC ACID

3)BAR MAGNET

4)MAGNIFYING GLASS

5)LEAD ACETATE STRIPS

6)10% COPPER SULFATE SOLUTION IN 89% DISTILLED WATER + 1% # 2

7)POCKET KNIFE

8)BUTANE LIGHTER

9)POCKET THERMOMETER

10)PLASTIC BAGS

11)DIXIE CUPS

12)SURGICAL SAFETY GLOVES

These tests must always be performed at a safe
location---completely removed from any oil and gas
location/pipeline. Follow the directions and safety
precautions for each test.
USES:
1) XYLENE- Take a small portion of the solids sample and add to a Dixie cup. Pour a small
amount of xylene onto the sample and gently stir. If sample begins to dissolve turning the
xylene from clear to brown or black, the solids have Hydrocarbons in them. One can then
take a separate sample onto the knife blade and gently heat it with the butane lighter. If the
solids sample begins to melt the solids are most probably a form of paraffin.
* Safety note- Do not use the open flame butane lighter near the flammable xylene or any
oil or gas location. Xylene fumes are hazardous and narcotic and should not be inhaled.

2) 15% HYDROCHLORIC ACID- Take a small portion of the solids sample and add to a
Dixie cup. Pour a small amount of 15% Hydrochloric acid onto the sample and gently stir.
If the sample begins to bubble gas and dissolve observe the color of the liquid acid in the
cup. If the acid remains clear, the sample contains Calcium or Magnesium carbonate. If the
liquid acid turns yellow or green, wet with water one end of a lead acetate strip and hold it
above but not into the liquid in the Dixie cup. If the lead acetate strip turns brown/black or
if a metallic shean is seen on the strip, Hydrogen sulfide is present.
This indicates that the sample contains Iron sulfide. If the acid turns yellow and the lead
acetate paper remains white take the bar magnet and touch it to the original dry sample, if
the sample is magnetic, the solids contain Iron oxide, Mill scale and/or processed metal . If
the acid turns yellow, the lead acetate paper remains white and the original dry sample is
not magnetic, the solids contain Iron carbonate. *Safety note- 15% HCL acid gives off
dangerous fumes and should not be inhaled. Any exposed skin or pipe surface should
immediately be washed with lots of water and soap.

3) BAR MAGNET- When applied to a sample of Iron oxide, Mill scale and/or processed
metal (steel) will show their magnetic properties.
 4) MAGNIFYING GLASS- When used to look closely at a solids sample can easily
identify irregular sand grains, pieces of man-made materials such as "0" rings and cotton
gloves and/or hexagonal (six sided) Calcium sulfate crystals.

5) LEAD ACETATE STRIPS- When moistened are used to identify the presence of
Hydrogen sulfide gas. Can be used for identification of Iron sulfide solids and other safety
related issues. *Safety note- Lead acetate strips contain Lead and should not be placed in
one's mouth. Lead is a hazardous metal and the strips should be disposed properly. Do not
use and throw down on the ground.

6) 10% COPPER SULFATE SOLUTION- When applied to a corrosion coupon or

any metal surface will immediately detect visually the absence of a coating and/or
corrosion inhibitor. Turns unprotected metal bright copper color on contact.

7) POCKET KNIFE- If left in " The Kit " can be very useful for performing these tests
and scrapping out a sample of solids from many locations. * Safety note- The knife
provided in " The Kit " is sharp and can cause injury if improperly used. Do not use any
metal object including the knife provided in " The Kit " in a manner that can cause a spark
in or around any oil and gas location and/or pipeline.

8) BUTANE LIGHTER- Is used in testing solids samples for melting or burning

tendencies. The butane lighter produces an open flame. Care should be excercised when
using this instrument on any solids sample or around any flammable liquid and/or gas.

9) POCKET THERMOMETER- Can test the relative temperature of practically anything.

10) PLASTIC BAGS- Can contain solids samples for transport.

11) DIXIE CUPS- Nice, disposable test vessels for solids testing.

12) SURGICAL GLOVES- Used to protect users of " The Kit " from the hazardous
chemicals contained and used therein.
13) COMMON SENSE- Not supplied in " The Kit " but necessary for use of same.
 Scale Coupons

Most scale coupons sent to this Lab will be of mild steel. The dimensions
are x 3", each containing three holes, in addition to the top hole which
is used to secure the coupon to the coupon chuck when it is installed in
a system.

Upon receipt of a scale coupon it will be coated with oil, CaCO3, Iron Oxide,
Iron Sulfide and various other materials. In order to determine which materials
are present and in what amounts, the following steps should be followed:

Scale Coupon Analysis

Equipment needed:
1. Analytical balance
2. Beaker (150 ml or 250 ml)
3. Hot plate
4. Drying oven @-160 degrees F.
5. Desiccator
6. Brillo pads

Reagents Needed:

1. Toluene
2. Distilled H2O
3. Acetic acid diluted 1:4 with distilled H2O
4. HC1 diluted 1:1 with distilled H2O
5. Acid Inhibitor
6. IPA

Procedure:

1. Weigh beaker on balance and record weight.

2. Place coupon in beaker and weigh together. Record Weight.
3. Fill beaker with Toluene until coupon is completely submersed and heat
gently on hot plate to a slow boil. Continue heating until all
hydrocarbon materials are disolved in the Toluene. Decant liquid and
repeat until Toluene remains light in color.
4. Dry beaker and coupon in drying oven. Cool to room temperature in
Desiccator and re-weigh and record weight. The weight difference are
organic deposits.
5. Fill beaker with 1:4 acetic acid. Heat gently on the hot plate to
a slow boil. Continue heating until sample stops effervescencing,
decant liquid, repeat if necessary.
6. Dry beaker and coupon in drying oven. Cool to room temperature in
Desiccator and re-weigh and record weight. The weight difference are
Carbonate deposits.
7. Fill beaker with 1:1 HC1 and acid inhibitor solution: (5-10% inhibitor in
1:1 HC1) to remove the iron compounds present. Heat gently on hot plate to a
slow boil, decant liquid, repeat until acid solution remains light in color.
Scale Analysis
i Continued
Page 2.

To Determine if iron sulfide (FeS) is present place a damp strip of

lead acetate paper over beaker when 1:1 HC1 solution is added. If
the paper turns dark FeS is present, report as positive or negative.

8. Dry beaker and coupon in drying oven. Cool to room temperature in

desiccator and re-weigh and record weight. The weight differences
are iron compound deposits.

9. Remove coupon from beaker and scrub clean using brillo pad and
water, rinse coupon in distilled water and damp dry. Place coupon in
beaker of Isopropyl alcohol to remove any water remaining. Dry coupon
and re-weigh, record weight.

Calculations:

1. Weight of coupon with scale equals weight of beaker and coupon minus
weight of beaker.

2. Total weight of scale equals weight of coupon with scale minus final
weight of cleaned coupon.

3. mg/sq. in = mg scale
factor

4. g/sq. in./year = (mg/sq. in) (10-3) (365)

days in system

5. mpy = (weight loss of coupon) (factor)

days in system

6. Composition of scale: Use the same calculations as are given

in the scale analysis procedure.
 NACE Standard T1A0374-90
Item No. 53023

National Association of Corrosion Engineers

Standard
Test Method

Laboratory Screening Tests to Determine the

Ability of Scale Inhibitors to Prevent the Precipitation of
Calcium Sulfate and Calcium Carbonate From Solution
(For Oil and Gas Production Systems)

The National Association of Corrosion Engineers (MACE) issues this standard in conformance
with the best current technology regarding the specific subject. This standard represents a
consensus of those individual members who have reviewed this document, its scope and
provisions. It Is Intended to aid the manufacturer, the consumer, and the general public. Its
acceptance does not In any respect preclude anyone, whether he has adopted the standard or
not, from manufacturing, marketing, purchasing, or using products, processes or procedures
not In conformance with this standard. Nothing contained in this NACE standard is to be
construed as granting any right, by implication or otherwise, to manufacture, sell or use In
connection with any method, apparatus, or product covered by Letters Patent, or as indemni-
fying or protecting anyone against liability for infringement of Letters Patent. This standard
represents minimum requirements and should in no way be interpreted as a restriction on the
use of better procedures or materials. Neither is this standard intended to apply in all cases
relating to the subject Unpredictable circumstances may negate the usefulness of this
standard in specific instances. NACE assumes no responsibility for the Interpretation or use of
this standard by other parties and accepts responsibility for only those official NACE
interpretations Issued by NACE In accordance with its governing procedures and policies
which preclude the issuance of Interpretations by Individual volunteers.

Users of this standard are responsible for reviewing appropriate health, safety, and regulatory
documents and for determining their applicability in relation to this standard prior to its use. This
NACE standard may not necessarily address aN safety problems and hazards associated with the
use of materials, operations, and/or equipment detailed or referred to within this document.

CAUTIONARY NOTICE: NACE standards are subject to periodic review, and may be revised or
withdrawn at any time without prior notice. NACE requires that action be taken to reaffirm, revise,
or withdraw this standard no later than two years from the date of Initial publication. The user is
cautioned to obtain the latest edition. Purchasers of MACE standards may receive current
Information on all standards and other NACE publications by contacting the NACE Publication
Orders Department, P.O. Box 218340, Houston, Texas 77218 (telephone 713/492-0535).

Approved November 1974

Revised January 1990
National Association of Corrosion Engineers
P.O. Box 218340
Houston, Texas 7 218
713/492-0535

Copyright 1990, National Association of Corrosion Engineers

T111011144110
Foreword
Scale can be defined as an adherent deptatit of inorganic compounds
precipitated from water onto surfaces. Meet oilfield waters are brines
containing large amounts of calcium saes. When calcium is depos-
ited as calcium carbonate or calcium sulfate. a lose of production and
increased maintenance expenses can result; therefore, scale inhibi-
tion is of primary importance to the of producer.
Scats inhibitors can be used in many circumstances to control
scats formation, thereby reducing production difficulties. Inhibitors
are commercially available and are widely used in of and gas
production systems. T'he test methods in this standard are designed
to provide a relative and quantitative measure of the abilities of
inhibitors to prevent the precipitation of solids, a necessary and
critical stage in the formation of scale deposits. The laboratory
screening tests descridid in this standard cannot and do not allow for
the wide variation in water chemistry and system properties seen in
field operations. As such they must only be regarded as a starting
point in the evaluation of scale inhibition products. The existence and
use of these methods allow for a uniform mode of collection of
screening test results and facilitates discussion of the results by
interested parties.
This standard, issued by NACE Group Committee T-1 on
Corrosion Control in Petroleum Production. was originally prepared
by Task Group T-10-9 and was revised by Task Group T-1D-31, a
component of Unit Committee T-1D on Control of Meld Conosion
by Chemical Treatment. The members of Task Group T-1D-31 are
consumers and producers of scale inhibitors and other interested
parties, who use NACE Standard TM0374 (latest revision) or a
modification of this standard on a regular basis.
The test methods in this standard have been selected by Unit
Committee T-10 as a means of comparing, under the specified
laboratory conditions, the effectiveness of inhibitors in preverang
precipitation of calcium sulfate and calcium carbonate from solution.
As the prices of such products change with time and may be
unkritem to the tester, no attempt has been made to dilute the
inhibitor to a common cost base.
Section 1: General
1.1 The test methods described in this standard are static laboratory
screening tests designed to give a measure of the ability of inhibitors
to prevent the precipitation of calcium carbonate and calcium sulfate
from solution at 160°F (71°C).
1.2 These test methods we recommended only for ranking the
performance of different chemicals under laboratory conditions set
by these methods. They we not intended to provide actual field
treating rates.
1.3 Many factors, such as reaction kinetics, fluid velocity and
composition. variable temperatures and pressures, scale adherence
and solids dispersion can significantly affect actual scale deposition
under field conditions. Detailed consideration of these parameters is
deemed to be outside the scope of this standard. However, field
conditions. field brine composition and other variables noted
above should be considered at some point in inhibitor evaluation
prior to final inhibitor selection for field use.
1.4 Tests should be conducted at various inhibitor concerti*** in
order to obtain a better comparison of inhibitors under labor elory
conditions set by these methods. The inhibitor concentration
mauled for a field applications fa* to be different than That debar -
tithed under these laboratory conditions.
1.5 This standard lists the necessary apparatuses, reagents. and
procedures for conducting screening tests.
Section 2: Calcium Sulfate Precipitation Test
2.1 This section lists the 2.2.3.3 Note: TM0374-90 forced draft oven or
apparatus and procedure for Insoluble materials immerse to 3/4 of
conducting the calcium in very small 2.3 Test Procedure their lengths in a
sulfate precipitation quantities will water bath at 160°F
screening test. remain after the (71°C) for 24 hours.
2.3.1 All tests are
specified reagents conducted on the
2.2 Apparatuses and have ccinOstaty inhibitor on an as- 2.3.7 Remove the
solutions
dissolved. For received basis; 1% test cells after the
corsislency of and 0.1% dilutions are 24-hour exposure
2.2.1 Constant
results, solutions made from the as- and avoid agitation.
temperature water shout/lbw filtered
received inhibitor. Allow the test cells to
bath or forced draft through a 0.45 cool to 77°F (25°C) s
oven with the capability micron filter. 9°F (5°C) for a time
of maintaining the 2.3.2 Using the 1%
not to exceed two
specified temperature and 0.1% dilutions,
2.2.4 Apparatus for hours.
within `2°F (1°C). pipet the desired
reproducibly delivering 50 amount of inhibitor
-Lt 0.5 mi., e.g., graduated 2.3.8 Pipet 1 ml of the
2.2.2 Clean and dust- into each test cell.
cylinders or volumetric test brine to a suitable
free glass test cells (4 Duplicates should be
pipets. vessel, avoiding the
oz [approximately 125 run of each
transfer of calcium
mL) bottles with a concentration.
sulfate crystals. and
positive sea). 2.2.5 One percent (wt)
dilute with distilled
deionized water solutions 2.3.3 Duplicate water, deionized
2.2.3 Synthetic brine of nhltribes ter be tested: blanks should be water, or as otherwise
prepared with distilled 0.1% (wt) inhibitor prepared as follows: specified in the
or deionized water, as solutions in deienized calcium determination
follows: water *aid be used for method to be used.
tests where inhibitor 2.3.3.1 Two
2.2.3.1 Calcium- loadings are to be betel* samples of the
containing 10 mg/l.... calcium-
brine: 7.50 g/L. containing
NaCI (ACS brine (50 mt.
2.2.6 Graduated
(American each) are set
measuring pipets in the
Chemical aside. The
following sizes: 0.1. 0.5
Society, blanks before
and 1.0 mL.
Washington, precipitation
D.C.] Reagent are determined
grade); 11.10 2.2.7 Standard reagents by measuring
g/L CaCl2 - and apparatus for the calcium ion
2H20 (ACS determination of calcium concentrations
Reagent grade). concentration as per ASTM (Paragraph
D 511-88 or D 1126-86, (1) 2.3.9) and
API RP 45,(2) "Standard dividing each
2.2.3.2 Sulfate-
Methods for the value by 2.
containing brine:
Examination of Water and
7.50 g/L NaCI
(ACS Reagent Wastewater (Part 300),"
3)
and other accepted test 2.3.3.2 The
grade): 10.66
meth ods. blanks after
g/L Na2S0, (ACS
precipitation
Reagent grade).
are prepared
and handled as
in Paragraphs
2.3.4 through
2.3.9 but do
not contain a
scale inhibitor.

2.3.4 Add 50 mL of
sulfate-containing
brine to the test cell
and mix well. Add 50
mt. of calcium-
containing brine to the
test cell.

2.3.5 Immediately
cap the test cell and
agitate to mix the
brines and the
inhibitor thoroughly.

2.3.6 Place all test

cells and blanks in a

NACE 4
 2.3.9 Determine the t b
calcium ion S e e
concentration by u r f
procedures given in l o
ASTM D 511-88 or D f p r
1126-88, API RP 45, a r e
"Standard Methods for t e
the Examination of e c p
Water and Wastewater i r
(Part 300)," or another R p e
accepted test method. e i c
NOTE: Calcium ion t t i
concentration values for a a p
duplicate test samples i t i
often differ by two n i t
percent or more. Some e o a
analysts consider a five d n t
percent difference to be ) i
unacceptable and to be i o
cause for rerunning the n 3 n
test 8 )
S 0
2.3.10 Report the o 8 5
1
average of the duplicate l
B 4
calcium ion concen- u
l 0
tration values as mg/L t
a
calcium sulfate retained i These data indicate that
n
in solution for each o inhibitor A is best. Note:
k
inhibitor test n Costs of the inhibitors
concentration and both have not been considered.
(
blank concentrations. (
a
2.3.11 Representative s
data from the
evaluation of three C
inhibitors are given in a
Table 1. These figures l
are examples only and c
do not reflect i
experimental precision. u
For a percent inhibition m
calculation, see Section
4. S
u
"ASTM. 1916 Race St.,
(
l
Philadelphia, PA 19103- f
1187. a
American
121
Petroleum t
Institute (API), 1220 L St.,
e
N.W., Washington. DC
20005.
,
American Public Health
(3)

Association. 1015 15th St.. m

KW., Washington. DC g
20005. /
L
)
T
A Scale
1 ppm 3 ppm 5 ppm
B Inhibitor

L
E A 5140 5140
B 4080 4352
1 C 4896 5103

— B
l
C a
a n
l k
c
i (
u a
m f
Section 3: Calcium Carbonate Precipitation Test
3.1 This section lists the 3.2.4 Fritted-glass gas
apparatus and procedure dispersion tube(s)
for conducting the calcium (medium or coarse
carbonate precipitation porosity rating).
screening test.
3.2.5 Synthetic brines
3.2 Apparatus and solutions prepared with distilled or
deionized water. as
3.2.1 A regulated follows:
source of carbon
dioxide (CO2). All
3.2.5.1 Calciuni-
recognized grades of
containing brine:
CO2 are suitable for
12.15 gIL CaCt2 -
this test
21120 (ACS
3.2.2 Constant Reagent grade);
temperature water 3.68 g/L MgCl2 -
bath or forced draft 6H20 (ACS Reagent
oven with the grade); 33.0 9.11
capability of NaCI (ACS Reagent
maintaining the grade).
specified temperature
within _t 2"F (1°C). 3.2.5.2
Bicarbonate-
3.2.3 Clean and dust- containing brine:
free glass test cells (4 7.36 g/L NaHCO3
oz [approximately 125 (ACS Reagent
mL) bottles with a grade); 33.0 g/L
positive seal). Caution: NaCI (ACS Reagent
The amount of vapor grade).
space above the test
solutions in Paragraph 3.2.5.3 Note:
3.3.6 will affect the test Insoluble materials
results. To maximize in very small
the validity and quantities will
reproducibility of test remain after the
results, choose test specified reagents
cells that vary in have completely
capacity (volume) when dissolved. For
sealed by 5% or less; consistency of
that is, V, = V i; 0.025 results, the
V, where V, equals the solutions should be
desired range of test filtered through a
cell capacities and V 0.45 micron filter.
equals the mean test
capacity.

2 NACE
•

TPA0374-90
 3.2.8 Apparatus for reproducibly delivering 50 ± 0.5 mL, e.g.,
graduated cylinders or volumetric pipets.
3.2.7 One percent (wt) deionized water solutions of inhibitors to
be tested: 0.1% (wt) inhibitor solutions in deionized water
should be used for tests with loadings below 10 ppm where
inhibitor loadings are to be below 10 mg/L.
3.2.8 Graduated measuring pipets in the following sizes: 0.1,
0.5. and 1.0 mL.
3.2.9 Standard reagents and apparatus for determination of
calcium concentration as per ASTM D 511-88 or D 1126-86,
API RP 45. "Standard Methods for the Examination of Water
and Wastewater (Part 300)." and other accepted test methods.
3.3 Test Procedure
3.3.1 All tests are conducted on the inhibitor on an as-
received basis; 1% and 0.1% dilutions are made from the as-
received inhibitor.
3.3.2 Using the 1% and 0.1% dilutions, pipet the desired amount
of inhibitor into each test cell. Duplicates should be run of each
concentration.
Rupture of the test cells has not been reported, yet it is a
potential danger associated with this test procedure. Note also
that an improperly sealed test cell may lead to pressure
release, a resulting test brine compositional change. and an
invalid test result.
3.3.7 Place all test cells and blanks in a forced draft oven or
immerse to 3/4 their lengths in a water bath at 160°F (71°C)
for 24 hours.
3.3.8 Remove the test cells after the 24-hour exposure and
avoid agitation. Allow the test cells to cool to 77°F (25°C) ±
9°F (5°C) for a time not to exceed two hours.
3.3.9 Pipet 1 mt. of the test brine to a suitable vessel, avoiding
the transfer of calcium carbonate crystals, and dilute with
distilled water, deionized water, or as otherwise specified in
calcium determination method to be used.
3.3.10 Determine the calcium ion concentration by procedures
given in ASTM D 511-88 or D 1126-86, API RP 45, "Standard
Methods for the Examination of Water and Wastewater (Part
300)," or another accepted test method. NOTE: Calcium ion
concentration values for duplicate test samples often differ by
2% or more. Some analysts consider a 5% difference to be
unacceptable and to be cause for rerunning the test.

3.3.3 Duplicate blanks should be prepared as follows:
3.3.3.1 Two samples of the calcium-containing brine (50
mL each) are set aside. The blanks before precipitation
are determined by measuring the calcium ion
concentrations and dividing each value obtained by 2.
3.3.3.2 The blanks after precipitation are prepared and
handled as in Paragraphs 3.3.4 through 3.3.10, but do
not contain a scale inhibitor.
3.3.11 Report the average of the duplicate calcium concentra-
tion values as mg/L calcium carbonate retained in solution for
each inhibitor test concentration and both blank concentrations.
3.3.12 Representative data from the evaluation of three inhibi-
tors are given in Table 2. These figures are examples only and do
not reflect experimental precision. For a percent inhibition
calculation, see Section 4.

3.3.4 Both the calcium- and bicarbonate-containing brines

TABLE 2 — Calcium Carbonate
should be saturated with CO2 immediately before using. Satu-
Retained in Solution
ration should be accomplished at room temperature by
(as Calcium Carbonate, mg/L)
bubbling CO2 through a bitted-glass gas dispersion tube
immersed to the bottom of the container. A rate of 250 Scale
rritimin. of CO2 for 30 minutes will be sufficient to saturate up Inhibitor 1 ppm 3 ppm 5 ppm 10 ppm 20 ppm
to 1 L of each brine simuttaneously. A tee may be used to spirt
the gas flow for this purpose.
A 3000 3400 3800 4000 4140
B 3500 4000 4100 4100 4100
3.3.5 Add 50 mL of bicarbonate-containing trine to the test cell
C 3600 4140 4140 4140 4140
and mix well. Add 50 mL of calcium-containing brine to the
test cell.
Blank (after precipitation) 2600
3.3.6 Immediately cap the test cell and agitate to mix brines and Blank (before precipitation)
inhibitor thoroughly. The cells must be capped tightly to avoid 4140
loss of CO2. Note: Pressure will build in the test cells as the CO 2- These data indicate that inhibitor C is best. Note: Costs of
saturated test brine approaches and reaches 160°F (71°C). the inhibitors have not been considered.
Section 4: Percent Inhibition Calculation
4.1 Caution: The percent
inhibition calculation is for
comparative purposes only. It
is not intended to reflect the
ability of a particular inhibitor
to prevent scaling in a field
application.
4.2 Percent inhibition values
may be calculated as follows:
Where:
C, = Ca2' concentration in the
treated sample after
precipitation Cb = Ca2*
concentration in the blank
after precipitation C, = Ca2 +
concentration in the blank
before precipitation

Inhibition
(I) = C•

Cb
x 100
C,
-
Cb
SPE 15457
SPE
SocietkorPetrolesznEncsneere

Use of Inhibitors for Scale Control in Brine-Producing Gas and Oil

Wells
by M.B. Tomson, Rice U.; L.A. Rogers,' Gas Research lnsL; K. Varughese, Aiquatani Pipe
Coating Terminal; S.M. Prestwich, U.S. DOE; G.G. Waggett, South Texas College of Law: and
M.H. Salimi, Rice U.
'SPE Members
This paper was prepared tor presentation at the blot Annual Technical Conference and Exhibition or the Swells , of Petroleum Engineers held
in New Orleans. LA October 5-8. 1916.

This paper was selected tor presentation by an SPE Program Committee following review of information contained in an abstract submitted by the autrorls).
Contents of the paper, as presented. have not been renewed by ihe Society of Petroleum Engineers and an Strisiect io correction by the autlyorni. The
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presented. Write Publications Manager. SPE. P O. Boa 933836. Richardson. TX 750113-3836. Telex. 730999 SPEDAL.
AB STR AC T methods to analyze IMTRODUCTIOM or down the
inhibitors in brine at annulus; and
Field and laboratory a low levels were Progress has been 4. squeezing
work sponsored by extended. A complete made toward inhibitor into
the Gas Research history of field controlling scale the formation
Institute (CAI) and developments and formation from in such a
the Department of the laboratory brines often manner that
Energy (DOS) have backup experiments associated with the inhibitor
shown that calcium- is inciuded in this geopressured energy will be slowly
carbonate scale paper. production, co- released when
formation in waters production wells, and production
produced with oil wells which make commences.
natural gas and oil large amounts of
can be prevented by References and water. As brine flows The first option,
injection of illustrations at end of out of the formation reduced production,
phosphonate paper. and up the well, the generally entails an
inhibitor into the pressure drops. This unacceptable loss in
formation, even if the pressure drop causes revenue. Injection of
formation is dissolved carbon inhibitors into the
sandstone without dioxide, CO2 to go surface equipment,
calcite binding out of solution, option 2, does not
material. Inhibitor which incr eases the protect the
squeeze jobs have solution pH. The pH production tubing,
been carried out on rise causes aqueous and installation of a
DOS's geopressuced- bicarbonate, HCOm downhole treat
geothermal Gladys to be converted to string, option 3, is
McCall brine-gas well carbonate. COm , often prohibitively
and GAI's co- which tends to expensive. The last
production wells in initiate calcium option, an inhibitor
the Hitchcock field. carbonate, CaC0s, squeeze, can protect
Following the precipitation either the near well bore
inhibitor squeeze on in the formation formation, the
Gladys McCall, the pore throats near production tubing,
well produced over the well bore, on and the surface
five million barrels of the production equipment.
water at • rate of tubing walls or in Successful inhibitor
approximately 30,000 surface handling squeeze jobs have
BPD without calcium- equipment. Four been
carbonate scaling. scale control
Before the inhibitor options include:
squeeze, the well
could not be 1. Limiting
produced above production
15,000 BPD without so that the
significant scale drop in
formation. In the Gil pressure is
brine-gas co- not
production field sufficient
tests, inhibitor to induce
squeezes have been precipitati
used to successfully on (see
prevent scaling. below for
details).
Laboratory work has 2. Injectio
been conducted to n of
determine what types trace
of oil field waters are concent
subject to scaling. ration
This research has led of
to the development of inhibito
a saturation index and rs in the
accompanying surface
nomograph* which equipme
allow prediction of nt.
when scale will 3. Injection of
develop into a trace
problem in brine concentratio
production. ns of
inhibitors
Core samples from downhole via
both fields were used a small
in laboratory studies diameter
and analytical treat string
2 Use Inhibitors for Scale Control in Brine-Producing Cas and Oil Hells
carried out on DOt's geopressured -geothermal
Gladys McCall brine-gas well near Grand Chanier,
La, and =I's co-production wells in the Hitchcock
field near Galveston, Tx, and will be presented.
The producing formation of the Gladys McCall well
was secondary quartz cemented and contained no
calcite, which made a successful inhibitor squeeze
design considerably more complicated. Previous
laboratory work has led to the development of a
method to predict when scale will begin to form
and how little inhibitor might be needed to
prevent stale.
In this paper we will first discuss the field
applications and results of phosphonate inhibitor
squeezes to prevent formation of CaCOs scale.
This will be followed by a description of
laboratory experiments and theoretical considera-
tions that led to the development of the
inhibitor squeeze techniques employed.
FIELD EXPERIMENTS GLADYS MCCALL
The first attempts at phosphonate inhibitor
squeezes at Gladys McCall were unsuccessful since
the inhibitor could not be pumped into the
formation. There appeared to be two possible
causes for this: (1) Poor surface water quality
with high iron and calcium content and (2)
Interaction of the phosphonate with formation
brine which contained 4000 PPM Ca ion (Table 1).
The first of these problems could be handled by
using good quality water which had passed through
an ion exchange and a good filtering unit to
remove any iron hydroxide. The second problem
could be handled by using a brine spacer ahead of
the inhibitor to force the calcium containing
formation water away from the well bore. Based on
these conclusions, the inhibitor pill was designed
to be injected as follows:
1. 300 B of 15% NaC1 spacer
2. 100 D of 3% inhibitor in 15% ■aC1 (the
inhibitor was nitrilotri(methylene
phospbonic) acid from Champion Chemical
Co., Houston, Tx
3. 100 D of 15% MaCI spacer
4. 100 B of 101 CaCla overflush
5. 500 B of 15% BaCI into the formation
as a pusher
6. The well was to be shut in for 24 hrs. to
allow reaction
In fact, 6% inhibitor was used (step 2).
Everything went well with the treatment at first.
Pumping rate was held at 2 IPS with only a slight
pressure increase over original shut in wellhead
pressure. When the 100 D of inhibitor hit the
formation, the pressure built up rapidly and the
pump rate was reduced to 1 DPW to keep from
exceeding fracturing pressure. The 100 D of
inhibitor and 100 D of NeC1 spacer was squeezed
away at 1 DPW.
When the CaCls overflush hit the formation, the
pressure built up rapidly to the pre-set limit.
Pump rats was reduced to 0.2 BPW and the 100 B
of CaCla solution was slowly pumped away. This
was followed by approximately 25 II of 15% NaC1
solution to clear the tubing. Then the well was
SPE 15457
shut in since all of the inhibitor was in the
formation and had been exposed both to calcium
from the formation brine and the CaC12 overflush
as evidenced by the pressure increases.
After 24 hours, the well was allowed to flow
back at 100 BPH. Brine samples were taken
every 10 barrels during the flow back of the
pill and periodically thereafter. These
samples were analyzed for numerous elements,
in addition to the inhibitor itself (Figure
1). It was found that magnesium was the most
distinctive tracer for the formation brine
although the early buildup (around 600 barrels
of returns) could be due to impurities in the
15% MAC' and some interaction with the
phosphonate. By the time 1200 barrels of brine
had been produced, Mg, Ca, Na and X had
stabilized to their original concentrations in
formation brine. About 70% of the inhibitor
flowed back with the first few thousand
barrels of brine production. The remaining
inhibitor was slowly released over the next
six months. The concentration of the inhibitor
dropped to about 0.1 to 0.2 mg/1 within a few
weeks and remained there until the well was
shut in for repair and resqueeze in January,
1986. This corresponded to about 701, of the
inhibitor remaining in the formation. In order
to measure such low inhibitor concentrations
in field brine it was necessary to modify
standard colormetric phosphonate procedures
which will be published elsewhere. Prior to
the inhibitor squeeze, production was limited
to about 15,000 BPD in order to avoid scale
formation. This severely curtailed gas
production. After the squeeze it was possible
to increase the production rate to about
30,000 BPD, still without scale formation in
the production tubing. During this period
about 25 SCF of natural gas was separated and
sold per barrel of brine produced. At about
four months into production, a light scale was
observed in the final filters before the
disposal well. This was eliminated by addition
of 0.25 mg/1 of inhibitor downstream of the
choke. After six months of production no
indication of scale formation in the
production tubing was found, and when the well
was shut in, the high pressure side of the
choke was observed to be scale free. Thus, the
phosphonate inhibitor squeeze had protected
the tubing for the production of over five
million barrels of brine.
Upon analysis of the breakthrough data of the
flowback curves from the first squeeze job, it was
concluded that the calcium in the formation brine
could be used to fors the calcium phosphonato in
situ if sufficient mixing could be obtained in a
large pill which was pumped a considerable distance
from the well bore. This would avoid the pressure
increase observed when the calcium of the CaCla
overflush hit the formation containing the pill and
would greatly simplify the overall operation of the
pill application.
Based on the observations from the behavior of the
first successful phosphonate inhibitor squeeze, a
simplified pill procedure was designed as follows:
1. Pump a 100 barrels preflush of 10% illaC1 to
push most of the Calcium ion in the reservoir
brine away from well bore.
SPE 15457 M. 8. Towson, ec al.
2. Use 100 barrels of pH neutral 3% (N1(4)
phosphonate inhibitor salt in 10% lad
solution which will react with calcium from
formation water.
3. Overflush with 900 barrels of 10% MaC1
followed by 300 barrels of oil field brine
to clean the tubing.
4. Shut in for 36 hours and bring back slowly at
100 barrels per hour.
5. After 2 days resume flow of 30,000 barrels
brine per day.
Since these fluids had approximately the same
density as the formation brine and viscosities
were low, the injection rate after preflush was
chosen as 6 barrels per minute.
An oxygen scavenger (MH4)HS0a and an iron
chelating agent (EDTA) was added to all of the
brine to prevent formation of iron hydroxide and a
2-1/2 micron filter was used just upstream of the
pump suction. In addition. 100 millicuries of I
131 was mixed with the phosphonate pill as •
tracer. The pressure curve for the injection is
given in Figure 2. No problem was encountered
which forced slowing the pumping rate. Maximum
pressure rise was approximately 400 to 500 PSI as
the pill was pumped into the formation.
The well was brought back on stream after 36 hours
and produced at the rate of 100 barrels per hour
for two days. Flow rate was then increased to
approximately 30,000 barrels and has remained
there for over six months except for a slow rate
decrease that is a function of the reservoir flow
properties.
Samples were taken on a regular basis during
early flowback and once a day thereafter. Figure
3 shows the 1-131 scintillation count data vs.
barrels of brine produced. A well defined curve
with a maximum at around 1450-1500 barrels of
brine flow results.
Samples of the brine were also used for
determination of the phosphonate concentrations in
solution. These are included in Table 2. In this
squeeze treatment there was never the tremendous
backflow of the calcium phosphonate that had been
observed in the earlier squeeze job. This is
probably because the phosphonate pill was pushed
far enough back into the reservoir to smear it out
over a large volume of the sand grains. After 8
days of production at 30,000 BPD the inhibitor
concentration dropped to about 0.15 ng/1 and has
remained at that level for over six months (Table
2).
The successful application of the phosphonate pill
has allowed the Gladys McCall well to be produced
at the maximum rate available from the reservoir.
Over five million barrels of brine have already
been produced using this second pill with
apparently no reduction in protection from CaCOs
deposition.
LABORATORY STUDIES AID THEORETICAL
CONSIDERATIONS
In order to prepare for the field work numerous
laboratory experiments were conducted. Core
3
material from the producing formation at the
Gladys McCall well was analyzed by x-ray
diffraction and by scanning electron microscopy
and microprobe analyses. Results are in Table 3.
From the information in Table 3 it can be
concluded that the producing formation is
sandstone cemented by secondary quartz with a
small amount of clay. The porosity was found to
be about 20%, similar to Brea sandstone. This
core material was used in all laboratory column
studies of the Gladys McCall well.
Column Studies
Column studies were conducted using both ground
core samples and intact core plugs. Packed columns
using ground core material were quick and easy to
prepare and allowed numerous variables to be
examined.
For the experiments using ground core material 14 g
portions of core material were gently crushed with
a porcelain mortar and pestle and packed into 10 ml
plastic pipets fitted for use as chromatography
columns. These columns were saturated with
synthetic brine (1 M l•Cl and 0.125
CaCla) and then flushed to remove all traces of
drilling fluids. These columns had 40% porosity.
After preliminary experiments were run to
determine appropriate concentration ranges, the
following test of the effect of CaCla overflush
was performed by injecting the following into a
set of columns:
1. 2.0 al 15% lad as a lead spacer
2. 0.5 al 3% active Gyptron T-132 (pH neutral
fora of Dequest 2000 from Champion Chas.
Houston, Tx.)
3. 0.5 al 15% lad as tail spacer
4. 2.0 al 15% Wel as overflush
These columns were shut in for 8 hrs at 85•C
(185•F) and than slowly backflushed with 40 al
of synthetic brine at 85•C. Columns were then
cut into 10 sections and each was analysed for
remaining inhibitor. Next, the 2 ml of 15% NaCl
overflush (4. above) was replaced by 2 al of 15%
CaCla. All experiments were run in duplicate, at
least. The overall mass balance of inhibitor in
these experiments was generally 901, or better.
A fourfold enhanced inhibitor retention is shown
in Figure 4 as a consequence of using a CaCla
overflush. This corresponded to about 40% of the
inhibitor which was loaded. For this reason a
CaCla overflush planned to be used is the
inhibitor squeeze at the Gladys McCall well.
Similar column experiments were conducted using
core material from the Delee No. 1 well in the
Hitchcock Field. These core materials were
calcite cemented. Little difference was observed
between the Nadi and CaCla overflush regimes.
Columns of intact Gladys McCall core metrial were
also prepared. Rectangular pieces of core material
1 cm x 1 cm x S ca were cut and embedded in Epoxy
in a 1 in OD steel pipe. The end cap pieces and
reducers on the pipe were all filled with Epoxy
end later drilled to allow 1/I" 00 high pressure
Teflon tubing to contact both ends of the
4 Cs. of Inhibitors for Scale Control in Brine-Producing Cas and Oil liens SPE 15457
core material (Figure calcium and
5). This system was carbonate,
used to evaluate the respectively, and
adsorption and Kip is the
conditional
desorption of
solubility product of
inhibitors. Columns
CaCO2.1 The solubility
were first saturated
product in Equation 1
with synthetic brine
is a function of
(1 M Nadi, 0.125 M temperature T.
CaCla, pH . 4.1) and
pressure P, and ionic
then flushed at 95'C strength IS, or total
until all traces of dissolved solids TDS.
drilling fluid were At the pH values
removed. A pill normally encountered
dosage of 0.95 ml of in sec-pressured
Ti inhibitor in 0.125 brines, the ionic
M CaCla and 1 M NaC1 calcium concentration
was injected into the in Equation 1 can be
core. The intact core replaced by the total
column was shut in calcium, Tca, which is
for 24 hrs at 95*C. easily measured. The
divalent ionic
Desorption of carbonate
inhibitor into flowing concentration, (C01-).
synthetic brine at in Equation 1 can be
95'C was monitored for expressed in terms of
about 10.000 pore bicarbonate (MC0a) and
volumes, or sixteen pH using the second
liters. The result is ionization constant of
plotted in Figure 6. carbonic acid. Below
After 300 pore volumes about 8.3 pH,
the inhibitor bicarbonate is
concentration dropped essentially the same
to about 1 mg/1 (as as alkalinity (Alk),
phosphonic acid) which is also readily
and remained measured. Finally, by
approximately appropriate algebraic
content for another substitution the pH
7000 pore volumes. can be expressed in
After about 7000 terms of Henry's law
pore volumes the constant, the
concentration of alkalinity, and the
inhibitor in the gas phase partial
brine rapidly pressure of carbon
dropped to below dixoide. Oddo and
detection limit. Towson (1962)1 have
determined least
Saturation Index squared curves for the
various equilibrium
The driving force for constants as a
CaCOa precipitation function of T, P, and
under any solution TOE. The SI for most
conditions can be gas and oil well
represented by the brines has been shown
saturation index, SI, to be:1
defined by:
SI • lea(Tc. 4)10/71,,,) •
bri SAII • 1.S0410'8 T
m?
sup - 4.21,00* T'
.ma
tur r - 2.556 Is% • 0.920
ati
mil, IS
soy
for
a where Tca(molar)
sca
le
0: (mg/1 Ca)/40.000; /ilk
mullibr
ium
(solar)
'co -: . (mg/1
HCO4)/61.000; IS
brie. tubseturated, scale
may istssohnt (molar) .
conductance
(vmho/cm)/66,667 m
(mg/1 TD6)/56,500;
where (Ca14) and (C0:-)
represent end ICOa volume or
mole fraction of
molar
concentrations of COs in gas phase,
with pressure, P,
in.psia end measureable. A simple
temperature, T, in kit to measure Ca,
'F. Alk, and TIM on site
is available from
 similar equation LaMotte Chemical Co.
for pH was
(Chestertown,
derived.' All of
Maryland) and the gas
the variables of
phase percent carbon
Equation 2 are
dioxide can be easily
readily measured by e.g.
Dreier tubes or gas
chromatography. The T
and P are generally
available at the
sample point. To
facilitate the use of
Equation 2 a monograph
was constructed2 and a
slide rule is
available from Shell
Canada (Calgary, Alta,
Canada). At initial
shut in conditions the
downhole SI in
Equation 2 is
theoretically zero for
any formation which is
calcite cemented.
Therefore, a change in
saturation index, ASI,
was defined as the sum
of the changes
resulting from P, T.
Ca, Alk, PCO,, and
TDS, independently:2
(31)
ASI • SI - SI,
sSIP • ASI,
aSIA,, • 15110. • &Sins
(31))
During production in
the absence of scale
formation the only
variables which
change from bottom
hole to well head
are T and P.
Homographs to
calculate ASI were
also developed.2 A
semi-quantitative
correlation of scale
formation process vs
SI was developed
from field and
- 7.44:10*
laboratory studies.
For ASI values
between zero and 1.1
to 1.4 scale will
probably not start
to form in equipment
free of scale. For
AS! values between
about 1.4 to 2.3
scale can generally
be controlled by
trace concentrations
of inhibitors. Above
ASI of about 2.3 it
may not be possible
to prevent scale
with inhibitors (see
below). Below ASI •
0 scale will not
form, but corrosion
will likely be the
prima concern,
especially if AU is
less than - 1.0.

Inhibitors

Rosenstein in 1935
found that extremely
low concentrations of
metaphosphates could
be used to prevent
scale formation.3
Today several classes
of compounds are used
for this
substoihiometric
(threshold) scale
inhibition, e.g.: 1.
inorganic
polyphosphates; 2.
polyphosphate esters;
3. phophonates; and
4. low molecular
weight polyacrylates;
and polymaleates.4

Most of these
threshold inhibitors
are surface active.
They probably prevent
nucleation of a new
scale phase by
interacting with the
forming nuclei and
preventing formation
of a stable solid
phase.5 They prevent
further growth of an
already existing
phase by adsorbing
onto active growth
sites on the surface
and preventing
incorporation of more
lattice ions.' For
brines supersaturated
with respect to
calcite it has been
proposed that the
lowest concentration
of threshold
inhibitor needed
would be
approximately the
molar concentration
of divalent
carbonate.
specifically:5

2(CO: -)/Iz(InS
-) < 1.0

where parenthesis
represent molar
concentrations and z
is the average charge
on the inhibitor or
inhibitor unit used to
express concentration.
The summation sign in
Equation 4 suggests
strict
SPE 15457 M. I. Tomos st 5
additivity of mixed distance awe), from In the second of the iodine has
inhibitors. In the well bore. This squeeze inhibitor returned by the time
laboratory tests can be done by test the iodine 3000 barrel of fluid
compounds and various carefully selecting peaks around 1500 have been produced.
combinations of the amounts of barrels (Figure 3)
compounds from several preflush to move the which is about 300 At flowing wellhead
chemical classes have brine which contains barrels later than conditions the
been shown to prevent calcium ion away from would be expected. concentration
nucleation at the well bore and It is interesting to inhibitor, 0.73 sg/1
concentrations similar pumping in excess note however, that (1.7 x 10-' N), is
to those predicted by afterflush to force if you integrate the only 15% greater
Equation 4. Yet, no the phosphonate into area under the iodine than that predicted
examples have been the reservoir where curve over 90% by Equation 4.1.3
found of inhibition of it interacts with This agreement may
calcite nucleation calcium from the be fortuitous, but
below the limit formation water to is similar to the
suggested by Equation form the insoluble lowest concentration
4. calcium phosphonste. found in laboratory
tests.1'4 As noted
Also, there is an There is considerable before, with each
upper limit at which room for improvement inhibitor squeeze
an inhibitor might in the development of scale began to form
work. This upper the inhibitor squeeze in.the low pressure
limit is controlled technique. For side of the surface
by the solubility of example, we are not equipment at 4 to 5 -
the inhibitor. sure that the 10% mos. This occurred as
Inhibitors of RaC1 preflush and the &SI increased
precipitation afterflush couldn't above 2.3 to 2.5
generally form be done with (Equation 3),1,2 but
insoluble salts of regularly available an additional 0.25
one of the lattice oil field brine. mg/1 of inhibitor was
ions of the phase Precautions would sufficient to prevent
being inhibited. All need to be taken scale in the low
of the classes of however to see that pressure region of
inhibitors listed the Ca and Fe levels the surface
above are anions and in the brine were equipment. When
form insoluble low. Also, the use of greater than 1 mg/1
calcium salts. If a small pore size of inhibitor was
the concentration of filter (preferably 2 injected in the
inhibitor is two microns or less) is a surface equipment
large a calcium- most to prevent calcium-inhibitor
inhibitor salt blocking of the well pseudoscale formed in
(pseudoscale) bore from any the filter units.
precipitates. For particles in the oil
some of the field field brine. CONCLUSIONS
systems investigated
by the authors this The mixing data 1. Phosphonate
upper limit of available from the inhibitor
inhibitor first squeeze can be
concentration has been successful squeeze used to
found to be only a few job at Gladys McCall successfully
mg/1 or less. is quite interesting. prevent
The sodium formation of
DISCUSSION
concentration (Figure CaCOs scale in
1) rises more sharply the tubing and
than expected and than surface
The development of • doesn't appear to
successful squeeze equipment of
remain at the high brine wells
method to inhibit concentration as long
calcium carbonate which would
as it should. In normally have
depositions from fact, the sodium
produced brines has scaling
concentration has problems.
been tested. This returned almost to
method has been shown Inhibitor
its normal formation concentrations
effective in sandstone brine level by the
reservoirs where of only 0.15
time 900 barrels of mg/1 have
there is no calcite brine have been
in the cementing effectively
produced, whereas prevented scale
material. The key we'd expect high
ingredient in a formation in the
values to cover at production
successful least a five hundred
application appears tubing.
barrel spread. Its
to be that the apparent peak at the 2. Treatments can
calcium phosphonate same point as the be
needs to be formed in
phosphonate peak also successfully
the reservoir at some
is unexpected. carried out in
 reservoirs
where the sand 1583-1590.
grains are not
cemented with 2. Tomson, N. B.,
calcite. Natty, J.,
Durrett, L. R.
3. Extreme care and Rogers, L.:
should be Saturation Index
taken to form Predicts Brine's
the insoluble Scale-Forming
calcium Tendency," cal
phosphonste salgag L. ga
in the (1985) pp. 97-
reservoir so 108.
that it won't
block the 3. Cowan, J. C. and
well bore. Weintritt, D. J.
Water
4. The use of a
calcium chloride
overflush can
be avoided by
using the
natural
dispersion
properties of
the reservoir
to induce the
mixing of the
injected
inhibitor with
calcium in the
formation
brine. This
greatly
simplifies an
inhibitor
squeeze.

Acisgtommigt
This work was
supported by the Gas
Research Institute
under contract No.
5084-212-0890, but in
on way does this
constitute an
endorsement by CRI of
any products or views
contained herein.
Manuscript preparation
by Leticia Villafranco
and artwork by Peggy
O'Day are gratefully
acknowledged.

Egnigang
1. Oddo, J. S.
and Tomson,
M. S.:
"Simplified
Calculation
of CaCOs
Saturation at
Nigh
Temperatures
and Pressures
in Brine
Solutions,
" J. Pet.
Tech.
(1982) pp.
 CONTINUOUS INJECTION OF SCALE INHIBITORS

Continuous injection is the preferred method for all scale inhibition

since it ensures the presence of proper levels of inhibitor at all times. In
this method, the chemical is applied with or without flush by a gas-
operated, beam-operated or electric chemical proportioning pump. For proper
addition, the scale inhibitors should always be injected into a stream of
fluid where adequate turbulence exists to ensure thorough mixing of the
inhibitor and to prevent stagnant precipitation of scale inhibitors.
Normally continuous feed of scale inhibitors in oil production is required
because the systems are once-through.

For continuous injection systems, the following are the inhibitor criteria:
the inhibitor must be completely soluble in the waters processed at usage
concentrations; unlike squeezing, precipitation in continuous injection should be
avoided. The solids add to the suspended solids and decrease water quality, as
well as promote scale deposition and underdeposit corrosion. The chemical should
not be corrosive to pumping equipment or to the system. The scale inhibitor must
be thermally and hydrolytically stable. They must be compatible with treating
chemicals in the production, processing and water systems; these include:
demulsifiers, paraffin compounds, microbiocides, corrosion inhibitors, surfactants
and other chemicals. The scale inhibitors do react with many amines, as the scale
inhibitors are highly anionic while the other compounds are cationic. Chlorine and
reducing microbiocides are also affected by (and affect) scale inhibitors and
subsequent performance.

Continuous injection scale inhibitors must not be pumped into static

brines due to precipitation potential. They should not be pumped directly
into water tanks, heater treaters or other vessels. Do not inject ahead of an
intermittent operating dump valve. Do not inject into annuli without adequate
flush. Do not allow faulty check valves to leak produced water into a scale
inhibitor line and do not pump scale inhibitors into lines containing neat
corrosion inhibitor. Do not drip feed scale inhibitors. Do maintain chemical
pump operation as it is critical to effective scale inhibition.

Scale inhibitors generally are injected at 5 to 100 ppm (typically 10 to

25 ppm) in scaling water to effect scale control. They must be injected as
far upstream of a scaling point as is feasible. The following are some of
the main points where scale inhibitors are applied by continuous injection
in the oil field: injection water systems, disposal systems, source wells,
producing wells, gas lift wells, flowing wells, hydraulic pumping systems,
heater treaters and other vessels. Start treatments high and reduce dosages
as possible.

The following are some of the generalized recommended continuous

injection programs:

1.Source wells-inject chemical down the annulus with slipstream flush at

10-25 ppm.
2.Gas lift wells-inject scale inhibitor highly diluted with fresh water
into the lift gas at 10-25 ppm.
3.Producing wells with open annuli-inject the chemical with slipstream
flush down the annulus at 15-100 ppm. Problems may occur with high
gas production or heading up and unloading out the annulus. A
macaroni string should be used for these problems.
Continuous Injection of Scale Inhibitors
Page 2.

4.Flowlines and laterals-inject the inhibitor at the head of the

line at 10 to 100 ppm.

5.Heater treaters-inject the scale inhibitor into the moving fluid

stream at the header or other point well upstream of the
vessel at 20-100 ppm.

6.Waterfloods and disposal systems-for scale problems downstream of the

station, inject the scale inhibitor in the pump suction at 10-25 ppm.
Where incompatible waters are involved, add the scale inhibitor to
the cation-containing water upstream of the comingling point.

7.Power oil or power water systems-continuously inject the scale inhibitor

into the power fluid at 10-25 ppm based upon water production volume
rather than power fluid circulation volume.

Special note: Do not attempt to add additional scale inhibitor (30-50 ppm)
at the injection station or injection wells to protect the
producing wells when brakthrough occurs as the scale inhibitor
would be adsorbed out within the formation. Unsuccessful
attempts have been made to to this.
 SCALE INHIBITOR SQUEEZES

Principles of Squeeze Treatments:

1. Scale inhibition, especially scale inhibition by squeeze treatments,
is an art not a science. It involves a certain amount of trial and
error and field experience in the development of viable squeeze pro-
grams because of the imcompletely understood mechanisms of scale
inhibition, the interactions between the chemicals and the water in-
volved and the complexities and unknowns in the formation.

2. For squeeze application of a scale inhibitor to perform for a desired

long-term life, the inhibitor must be retained in the formation by one
or more retention mechanisms: adsorption, and/or precipitation.

Adsorption-a physical interaction between an ionized solution and a solid

surface in which molecular forces promote a molecular film by
charge attractions between the ions and the solid surfaces.

Precipitation-the formation of an insoluble salt from solution by reaction

between anion (scale inhibitor) and a cation (divalent metal
salt, usually Calcium).

3. The inhibitor retained in the formation must be capable of desorption

from the formation surface at a slow enough rate to allow long-term '
inhibition.

4. Adsorption-desorption is the preferred mechanism in scale inhibition in a

formation since precipitation involves the development of potentially-
plugging precipitates which could cause long-term or permanent formation
damage.

5. In essence, the application of a scale inhibitor squeeze is a batch treat-

ment; however, the performance of the squeeze is a continuous treatment.

Requirements of Squeeze Application Inhibitors:

1. The inhibitor utilized must be effective against the scale(d)

involved at a low dosage.

2. The inhibitor must have adequate adsorption-desorption characteristics to

allow a long-term continuous inhibitor return.

3. The inhibitor must be thermally and hydrolytically stable for long

terms under formation conditions.

4. The inhibitor must be compatible with the produced fluids, the formation
lithology and other chemicals utilized in squeeze, well treatment and
production processing.

5. The inhibitor must not promote or create emulsification.

6. The inhibitor in return fluids must be monitorable at low typical

usage concentrations.
Scale Inhibitor Squeezes
Page 2.

7. Other desirable properties could include solids dispersion

capabilities and water-wetting (oil dispersion).

Mechanics of Scale Inhibitor Squeezes:

1. A formation squeeze is the placement of a chemical or chemicals into

a formation at pressures and rates which are less than fracture
pressure for a given formation.

2. Scale inhibitor squeezes are determined arbitrarily, or they have

been established by trial and error in field applications.

3. The amount of inhibitor required, the volume of overf lush, and the
use of diverting agents or other additives will depend upon:

a: Well completion data.

b.Amount and flow rates of produced fluids.
c.Field experience.

4. Because of the complexity of environments and array of production

conditions, there are a number of methods utilized for inhibitor
placement in the formation:

a.Adsorption squeeze.
b.Precipitation squeeze.
c.Forced precipitation squeeze.
d.Fracturing placement.
e.Mixed adsorption-precipitation squeeze (most scale squeezes are
probably of this type. Actually, a combination of A &

5. In order for a squeeze treatment to provide maximum benefit, existing

scale (and paraffin) deposits must be removed.

6. Potential problems resulting form scale squeeze:

a.Formation of a "pseudoscale" due to interaction of improperly applied

inhibitor with divalent metal cations in formation brine (Me", Ca++, Ea+
+, Sr44). Results are scaling, plugging solids and loss of scale
inhibitor.

b.Emulsions created by surfactancy of some scale inhibitors, especially

phosphate esters. Results are decreased productivity following squeeze,
presence of chemical emulsion in production and increased demulsifier
and heat requirements for oil treating.
c.Emulsion blocks are possible anytime foreign fluids are placed into a
formation. In addition to, and in relation to, emulsion blocks are
the development of zones of water saturation. The result is a loss
of production following treatment.
Scale Inhibitor Squeezes
Page 3.

7. Basic Operation of a scale squeeze:

a.Mixing of inhibitor and diluent at a suitable ratio and pumping

down tubing or annullus.

b.Displacement of the inhibitor to perforations or open hole face.

c.Overdisplacement of the inhibitor into the formation several

feet from wellbore.

d.Shut in period to allow maximum adsorption of the inhibitor

and migration of the balance into pores, vugs, fractures and
other traps.

e.Monitoring of produced brine for inhibitor

return. Designing Scale Squeeze Treatments:

1. Scale inhibitor squeeze treatments must be designed for specific conditions

on a well-by-well basis. There is no such thing as a standardized squeeze.

2. Only a properly designed scale squeeze will be effective. Application of an

optimum inhibitor by improper procedure will result in poor performance or
squeeze failure.

3. Scale inhibitor squeezes can be designed for any formation composition-

limestone, dolomite, sandstone, or shale. Returns from sandstone may be
75% or more of the inhibitor during the effective life, 50% or more in
limestones and as low as 25% from dolomites. Returns usually improve
significantly with future squeezes.

4. The following are the design features of each type of squeeze application.

(a)Adsorption Squeeze-preferred squeeze mechanism in which an inhibitor is

placed into the formation and the chemical is
adsorbed to the formation matrix. Effective in all
formation types.

(b)Precipitation squeeze-a squeeze in which the acid form of a scale inhibitor

is placed in the formation or basic form is mixed with
15% acid and placed in the formation. The acidic scale
inhibitor or the HC1 acid reacts with calcium carbonate
in the rocks to produce a high level of calcium ion in
the solution to promote precipitation of a calcium
phosphonate salt which will slowly solubilize as an
effective inhibitor. Effective only in limestones,
dolomites or calcareous sandstones and calcareous shale.

(c)Forced precipitation squeeze-a modified precipitation squeeze which utilizes a

calcium chloride solution pumped in the treatment to
precipitate the phosphonate salt. Used in non-calcareous
sandstones and shales.
Scale Inhibitor Squeezes
Page 4.

(d) Fracturing fluid placement- a scale inhibitor determined compatible with

the frac fluids is placed into the formation, pumped at
frac pressure and adsorbed or precipitated in the newly
developed porosity or fractures. Serves as an initial
squeeze.
 SPECIFIC SCALE INHIBITOR SQUEEZE DESIGNS

I. Inhibitor Volume:

The first step in developing a scale inhibitor squeeze treatment is to

determine how much of the selected scale inhibitor is required. The following
calculations allow determination of approximate inhibitor dosages. Normally a
minimum of 55 gallons is recommended.

A. Radius of Desired Protection (most accurate and preferred procedure)*

SI = (Rp 2 - Rw 2 ) xlrx8x TXC
or SI = 0.785 (Rp2 -Rw2) x 8 x T
where SI = scale inhibitor volume in gallons
Rp = radius of desired protection (feet)
Rw = radius of wellbore, casing 0.D., or openhole in feet.
?r= 3.14
8 = porosity of formation expressed as a drcimal.
T = thickness (length) of pay zone in feet.
C = constant; 0.25 based upon experiment results and squeeze case histories.
* Use this equation for high volume wells or wells with considerable pay zone.

B.Estimated Life Based on Production

SI = VwxDxC
where SI = scale inhibitor volume in gallons
Vw = water production, bwpd
D = estimated or desired squeeze life, days
C = constant; 0.006 based upon experimental results and
squeeze case histories

C. Rule of Thumb for Inhibitor Volume

0.62 to 0.7Z of daily water production; 12 in lower volume wells

Use no less than 55 gallons per squeeze.
BPD x .008 = drums of chemical (12 of H2O prod.)
BPD x .006 = drums of chemical (0.72 of H20"prod.)
BPD x .005 = drums of chemical (0.62 of H2O Prod.)
42
(based upon 55 = 0.8; 1% = 0.008)

II. Displacement Volume:

Use the tubing or annular displacement tables in a Halliburton, Dowell
or B J-Hughes cementing manual. Use produced water or 2% KC1. Be sure
to include 0.1-0.52 suncrwr
Specific Scale Inhibitor Squeeze Designs
Page 6. •

III. Overdisplacement Volume:

As a general rule, the amount used is equal to one (1) full days water
production, with a 100 barrel minimum (at least 6 foot radial penetration).
Do not use more than 250 to 300 barrels except under specific recommendation.
Produced water or 2% KC1 brine should always be used. Be sure to include 0.1
to 0.5% SURFAcIRAPT.

Radial Penetration (ft.) Over Displacement (BBLS)

1 2
3 23
5 66
6 100
7 130

9 215

IV Inhibitor Dilution Volume

Normally, Acci,r...v.recommends 10% in fresh water; some companies

recommend 2.5% for phosphate esters and 5% for phosphates in fresh
water or produced water.
b. If produced water must be used, the proper dilution ratio must be
determined with the scale inhibitor added to the water to determine
solubility range. Check 1%, 5%, 10% and 20% until a ratio with a
clear solution is achieved. Produced water is normally used only
when no fresh water is available or due to the presence of water-
sensitive clays or shale; ACc1;/"41-prefers the use of 2% KC1 brine
in these situations rather than produced water.

V. Shut-in Time
Based upon proven field performance, the shut in time to allow maximum
adsorption and migration of the inhibitor should be 24 hours. Some
companies may recommend 48 hours, but field experience by several
companies have shown excessive time provides no discernible benefit. No
less than 12 hours shut-in should be recommended; 24 hours is preferred.

VI. Typical Adsorption Squeeze Procedure (no packer)

1.Collect acidized water sample for baseline in residual monitoring.

2.Conduct recommended well clean-out.
3.Close the offside casing and flowline valves and pressure the tubing
to 250 psi by pumping 2 to 3 strokes to fill the tubing.
4.Shut the unit in on downstroke.
Specific Scale Inhibitor Squeeze Designs
Page 7.

5. Pump 10 to 30 barrels of clean produced water or 2% KC1 brine

containing 0.5% suRFAc-r4/47- down the annulus.

6. Mix the recommended scale inhibitor volume in fresh water at

a 10% ratio of chemical and pump the mixture down the annulus
at a rate below frac pressure.

7. Displace the inhibitor-diluent mixture to the perforations or

open-hole face with the required volume of produced water (or 2%
KC1) containing 0.5% b.v. SURFACT4A)-7-;

8. Overdisplace the inhibitor-diluent mixture into the formation with

produced water (or 2% KC1) containing 0.5% b.v. SURFAcro4Afir.
Volume should be 100 to 300 barrels depending on the daily
water production.
9. Shut the well in for 24 hours and remove treating equipment.
10. Return the well to production and begin monitoring program.

Note: For wells producing under packer, the treatment must be down the tubing.
As a result, the pump must be unseated in a rod-pumped well to allow
passage of treating solution. Displacement volume will change.

VII. Staged Inhibitor Squeeze (for wells with large open hole area):

1. Collect acidized water sample for baseline in monitoring.

2. Conduct recommended well cleanout.

3. Premix the recommended scale inhibitor at a 10% ratio in fresh water or

2% KC1 brine and pump 50% of this mixture down the annulus.

4. Pump a 50 barrel pad of water down the annulus.

5. Pump 10 to 20 barrels of diverting agent (typically SO to 100#) down the

annulus. The volume necessary will raise the pressure about 150 psi.

6. Pump the remaining scale inhibitor mixture down the annulus.

7. Displace to the perforations with produced water or 2% KC1

containing 0.5% b.v. SURFAc7rAr,11-;

8. Overdisplace the mixture and diverter into the formation with 100
barrels of produced water or 2% KC1 containing 0.5% b.v. SURFA°CrAttn:

9. Shut the well in for 24 hours.

10. Return the well to production and begin monitoring program.

Specific Scale Inhibitor Squeeze Designs
Page 8.

VIII. Typical Precipitation Squeeze:

1. Collect acidized water sample for baseline in monitoring.

2.Conduct the recommended well clean-out.

3.Shut the offside casing and flowline valves.

4.Pressure up on the tubing to seat the pump and prevent leak-by.

5. Mix the recommended dosage of phosphonic acid in fresh

water or 2% KC1. Add acid retarder, if needed, at 1% of
scale inhibitor volume.

6. Pump the scale inhibitor/diluent mixture down the annulus at

adequate pump rate below frac pressure to ensure maximum
penetratin of the formation.

7.Displace the inhibitor to the perforations or open hole face

with required volume of produced water or 2% KC1 containing
0.5% b.v. P. FACTRArr.

8. Overdisplace the inhibitor into the formation with 100 to 250 barrels
of produced water or 2% KC1 containing 0.5% b.v. SURFAC74e1:

9. Shut the well in for 24 hours to allow maximum acid neutralization

and precipitation.

10. Return the well to production and initiate the monitoring program.

IX. Typical Forced Precipitation Squeeze

1.Collect acidized water sample for baseline in monitoring.

2.Close in offside casing and flowline valves.

3.Pressure up on the tubing.

4.Premix the phosphonic acid with 2% KC1 brine or fresh water at 5%

to 10% (optimum) ratio.

5.Pump the mixture down the annulus.

6.Displace the scale inhibitor-diluent mixture with a 1% CaC12

brine (4 lb./barrel).

7.Overflush the scale inhibitor-diluent with 2% KC1 brine or fresh

water containing 0.5% b.v. PAR Vitt.c-rott4T to the recommended
radial penetration.
Specific Scala Inhibitor Squeeze Designs
Page 9.

8.Shut the well in for 24 hours (optimum).

9.Put the well back on production and initiate monitoring

program.

X. Monitoring

Monitoring of the organic phosphate scale inhibitors (phosphate esters,

phosphonic acidized phosphonates) can be done by collecting an acidized
water sample on at least a monthly basis. Analysis should be ppm of
proprietary compound although some chemical companies run total phosphate
(no distinction between ortho- and metaphosphate). Polymer residuals are
run by specialized procedures (carbonate adsorption bed or dialysis
methods), and should not be acidized. Results should be reported on a
running report form or graph showing squeeze dates.

TYPICAL RETURN CURVE

Inhibitor Return
Time in Days or Months --->
 TABLE
COMPARISON OF ADVANTAGES AND DISADVANTAGES OF
INHIBITOR SQUEEZES AND DOWN HOLE TREAT STRINGS

flmarroR sauEgiE
 Achraniacuti
1.Treat near wel bore formation to
prevent plugging during draw down.
2.All staid surfaces at the well bottom are
protected from scale.
3.A squeeze can be done on old wells
without puling tubing.
4.During routine production, tittle
maintenance Is required and no
on-site power is needed.
5.Generaiy, a squeeze is a simple
procedure for most service
comparies.
6.The potential lifetime of a squeeze is
virtually unlimited, in theory.
7.Only periodic (about weekly) brine
analysis is necessary to detect
when to resqueeze.
Disadvantages
1. A squeeze generally must be repeated
from every two weeks to two years.
2. The rule-of-thumb is that only about
one-third of the added inhibitor is
actually effective: one-third generally
flows back with the first production
and about one-third is never returned,
although these ratio may improve
upon repeated squeezes.
3. There is virtually no control on the
concentration of inhibitor which flows
back with the brine.
4. Performance on a new system
is highly unpredictable.
5. Once a squeeze is started, It is not
possible to change the concentration
or the chemical, as it is with a treat
string.
6. There is a real potential for
formation damage.
7. It is difficult and expensive to treat
corrosion due the different chemical
nature of corrosion inhtitors and the
higher concentrations often needed.
8. It is difficult to analyze for most
scale inhibitors at the
concentrations typically needed.
DCMIWQLEIBEALSIERISI
Achlaff1808s addition Dis 5. The
al treat adv presenc
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and to s dips,
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ration addition 1. The treat complic
can be al string ate
change chemical tubing, some
d as problem generall mainte
s, such y one- nance
needed.
as fourth in. operati
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n and stainless
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2. Deivery
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ation is nhol
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and can com
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product fails,
ion rate per tube
it is
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Axle n of
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can be treat
monitore strin
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or by res a
Inferenc work
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4. Tre
at 3. Operatio
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If reliable
°ti on-site
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is Loss of
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 IMILL1
The Conditional Sokibilties and Stoichlometdo Coeffidents
for Ca - Dlethylenetdaminepenta(Methylene Phosphonate)
in 2.0 M Brines at 70° C
pH Stoichiornetric Conditional
Coefficient Solublity (K1

4.7 0.50 4.27 x 104

5.0 0.48 3.02 x 104
6.0 0.41 1.92 x 104
7.0 0.30 1.78 x 104
8.0 0.31 1.23 x 104
9.0 0.29 1.20 x 104

SOLUTIONS ARE CHEMICALLY ACTIVE AND EITHER

SCALE OR CORROSION DOMINATES
BrALLIAMEDIAIEPHOLEM
CORROSION: LONGER TO DEVELOP
GA S
01L

—SOIL
 X___________BRINE
SCALING TINCENCY NCR. DRAMATICALLY AFTER CHOKE

TEMPERAURE ESSENTIALLY CONSTANT

PRESSURE DECREASING
SCAUNG TENDENCY INCREASNG
CORROSION TENDENCY DECREASIVG
SC DS CAN PLUG
DISPOSAL RESEVOIR

si N:stszsA:sr

;;, t t Si t 1 i t ft t it'~ti
 CORROSION GENERALLY
A PROBLEM DOWNHOLE

PRESSURE
DEREAS1NG N
RESEVOIR

CONVENTIONAL CURES
PARAMETER SCALE CORROSION
TaFERATURE DEC. DEC.
PRESSURE INC. DEC.
PH DEC. INC.
SATURATION INDEX DEC. INC
DISSOLVED SALTS INC. DEC.
CHEMICAL ADDITIVES
MALE Ca180614N
PHOSPHONATES AMINES
POLYACRYLATES THIO-AMINES
POLYMALEATES FATTY ACIDS TO 1 000mg/1
AT 1-10 mg/1 ZINC CHROMATES
PROTECTIVE SCALE
FIGURE 1. SCHEMATIC DIAGRAM OF A PRODUCTION SYSTEM
•

THRESHOLD MOTORS MAY NOT WORK ABOVE SI 2.3

RANGE WHERE SCALE CAN PROBABLY BE

2.0
CONTROLLED MTH CHFJAICAL
INHIBITORS

TRANSMON RANGE FROM NON-SCALING

TO SCALING

1.0

RANGE WHERE INHIBITORS ARE PROBABLY NOT NEEDED IN A

SCALE FREE SYSTEM

EQUILIBRIUM
0.0

SCALE WILL NOT FORM BELOW SI 0.0

SCALE WILL DISSOLVE AND BRINE MAY BE VERY CORROSIVE BELOW SI

-1.0 1 .0

FIGURE 2. DEPICTION OF SI VALUES AND

CORRESPONDING SCALE-RELATED PHENOMENA FOR
CALCIUM CARBONATE, SCALE FORMING BRINES

Patiel110401011/.00,0W,PHH Polyetnylaneglyco4nnonOnnto

wo AT ester PE-22
0
Cipost 2000
--- OH

14+0/44HTeM1004nr1.1-410004014:44 40/12
HEM HO 014 OH tiszed phosphonairearboxylate AHsPO,Ns,
I 8 1
HO— P—C — • — OH 14000C(CH24— N
Ostn.Ht2ow a I VITC-08 \CH*P03HP4a
0 CH. 0

44041.04.
CHNC,00.1
044441'1444041.1.40ents\ Cnrle PC/0 HO —C—
04044410n4 200soitax Pe:01 )1 04.04. 24 CHICHI .4,..
I
4404,044 CHI CH.P0s14 COOH
04011411 20110
PO•14. CH/000H

N ais
101.10110eCa.°4"W VITC-10
2144:1444 300
csoPosmil
-Om COON A

Ptanotorals 00,044,
1 01—,04).-14-404).
WTC-11 1 I
C. CH,

FIGURE 3. SOME COMMON THRESHOLD SCALE INHIBITORS

CHEMICAL CHEMICA
RESERVOIR L
INJECTIO
N

VALVE 0

FILTER

VALVE

TREAT
STRING

RUPTURE DISK

CHECK VALVE [

FIGURE 4. SCHEMATIC DIAGRAM OF BASIC

INHIBITOR TREAT STRING APPARATUS
 CALCIUM SULFATE (GYP) SCALE REMOVAL CHEMICALS

Scale type deposits have probably been occurring in well bores and surface e-
quipment since the beginning of the industry. The literature shows investi-
gations on paraffinprOblems as early as 1923. (1) And there is a reference for
acid being used in wells for, "... dissolving out limestone that has been
deposited from the waters...", in Oklahoma in 1928. (2) Generally the inor-
ganic scales were assumed to be calcium carbonate. Where these scales formed
they were considered more of a nuisance than a serious problem. The standard
solution was acidization of the well and equipment.

With the advent of waterflooding and particularly in dolomitic reservoirs, it soon

became apparent that, in addition to carbonates, sulfate scales were formed. The
principal scale was calcium sulfate with barium and strontium types being
occasionally encountered. Since these scales were essentially insoluble in acid
the usual treating procedures were no longer effective. It further became apparent
in the sixties, that when these scales formed on the reservoir face and in
perforations, the productivity of wells would be markedly reduced. As the
seriousness of the calcium sulfate problem was recognized there was a concerted
effort by both producers and service companies to develop treating chemicals and
procedures to solve the problem.

EARLY FIELD EXPERIENCE

With the damaging effect of scale formation on well productivity fully recognized a
major sales effort was directed to this problem by chemical suppliers. In a survey
conducted in 1962, twenty-two chemical suppliers were marketing 93 commercial
formulations for the prevention or removal of scales. These ranged from well known,
low priced materials to complex blends of organics with alleged esoteric actions.
Many of the early well treatments failed and by the mid-sixties it was estimated
that only 50% of the programs for removal of sulfate scales were even partially
effective. A survey conducted in the late sixties listed 35 chemicals being
furnished by fifteen suppliers for. the removal of well deposits of sulfate
scales. It was obvious from field results that either many of the chemicals were
not effective or well treating procedures were inadequate.

The extent to which calcium sulfate deposits can impair production of a well
is shown by Figure 1, for the period 1961 to 1967. Also it will be noted in
 2

Figure 1 there is wide variations in the effectiveness of the clean out proce-
dures, further emphasizing either chemical or treating method inadequacy. In
view of frequent treating failures and erratic results,in depth studies of the
problem were required.

LABORATORY STUDIES ON CALCIUM SULFATE REMOVAL CHEMICALS

In the late sixties the laboratory of a major producer began an evaluation

of the effectiveness of chemicals being sold for gyp scale removal.
Fifteen suppliers furnished 30 chemicals for the tests.

The initial program was a screening type to determine which of the chemicals
exhibited sufficient activity to warrant additional evaluation. The criteria
for passing this test were arbitrarily selected as:

A - Effective with a dilution rate of 1:1 with water.

B - Compounds formed must be either water or acid soluble.

C - Reaction independent of pressure (no CO2 evolution).

D.- Effectively convert 75% of scale to a soluble form.

The screening tests were on 1/2 inch cubes cut from gypsum rock consisting of
fine needle like gyp crystals andarorphous CaSO4 powder. While it was recog-
nized the rock was not comparable to the frequently encountered crystal form,
it had many advantages for a screening test. The samples were of a uniform
composition and test blocks could be precisely sized. The high porosity and
permeability furnished a maximum of surface area for reaction.

The bottle results shown in Figure 2 are typical of the performance of many of
the chemicals. By visual observation only, the treated sample indicates the
reaction has been extensive. But as shown by the test results in the third
bottle the rate of conversion has been quite low. As shown in the Table at the
bottom of the Figure only four of the chemicals evaluated met the specifi-
cations that had been established for acceptability.

In view of the inadequacy of most of the chemicals the suppliers were informed
of results on their materials and comments requested, permission was also grant-
ed to submit additional chemicals for screening. Some suppliers objected to the
type of rock used in the testing and it was agreed to conduct future tests on
other forms of calcium sulfate.

In the second test program 31 chemicals were submitted for evaluation. The testing
method was identical to that described for the first program, illustrated in
Figure 2. However to assure the form of the calcium sulfate was not influencing
the results three variations were used. The rock type used previously, thin clear
bladed crystals from a pipe in West Texas carrying Hendricks Reef water, and crys-
tals deposited in tubing in a New Mexico well. The latter were of a variety of
shapes and sizes. In the tests they were broken and graded to approximately the
size of pea gravel.

The test procedure was identical to that presented in Figure 1, except the
chemical was used at a 100% concentration. Of the 35 chemicals tested 23 met
the requirement for 75% effectiveness.
 3

The second screening test was to determine the dilution effect. In most wells
the area to be treated will be filled with produced water. Also in many treat-
ments, where a long producing interval is to be covered, it is desirable to di-
lute the chemical. The criteria for acceptance was that 75% of the scale must
be converted to a form soluble in water and/or acid at a 1:1 concentration of
the chemical. Figure 3 illustrates typical results on the chemicals meeting
this specification and outlines the test procedure followed.

This test eliminated 12 of the 23 chemicals. The 11 chemicals meeting the

specification all gave results in the 95 to 100 percent efficiency range.
The type and speed of reaction indicated all these chemicals to be of the
same generic family and of the same approximate concentration. Also the
results were so markedly superior to the other 12 chemicals in the program
that no further testing was warranted on the other products. The 11 satis-
factory products were from nine major chemical supply companies. This as-
sured the availability of a suitable product in all major producing areas.
This program established the effectiveness of chemicals and eliminated this
as a potential source of treating failures.

FACTORS CONTROLLING SCALE DEPOSITS (3, 4)

Once it became recognized that calcium sulfate scales could be plugging the
formation there was a tendency to over react. Many operators, without adequate
study assumed any abnormal production rate decline was caused by scale
deposits. While the ineffectiveness of many of the chemicals resulted in
failures, unfortunately many wells were also treated where scale was not the
problem. However as the factors governing the precipitation of calcium sulfate
scales became more generally known the treating of wells where scale was not
the problem markedly decreased. The following discusses the principal items to
be reviewed in evaluating the scaling possibilities in a well or field.

RESERVOIR ROCK CHARACTERISTICS: It would be assumed that the water, both in the
interstices and formation outside the reservoir, would be saturated with the
soluble salts contained in the producing interval. The usual mineral sources of
the calcium and sulfate ions are anhydrite, gypsum and hemihydrate. If any of
these minerals are present it would be assumed the waters contained in the
reservoir are saturated with calcium and sulfate ions for the pressure and
temperature conditions of the reservoir. It should further be assumed, in flood
projects, regardless of the injection water composition, it will become
saturated with calcium and sulfate ions, where the above minerals are present,
as it moves from injection to producing wells.

When calcium sulfate containing minerals, are present in the reservoir, scale
deposits should be anticipated during the producing life of the field. However
the deposits may be in the producing equipment rather than the well bore. Also
the time period over which scales occur will vary with water composition and
pressure and temperature conditions in the flow stream,- --

TEMPERATURE EFFECT: The curves on Figure 4 show the solubilities in distilled

water of the three mineralized forms of calcium sulfate at various temperatures.
While the form and relative position of the curves would be expected to remain
the same, the solubility values will change with pressure and other dissolved
salts. The relationship between the gypsum and anhydrite illustrates why both
types of scales will be encountered in production operations. For the conditions
of the curve, at temperatures less than approximately 100°F., gyp crystal
 4

scales will develop. Above this temperature the anhydrite should be expected.
Since in most wells the temperature drop between reservoir and well bore would
be insignificant, this factor is not considered important in most well bore
deposits. But as will be noted the solubility of gypsum drops significantly
below 100° F. This probably accounts for the heavy crystal deposits in some
systems where the surface temperatures in pipelines are below the produced
water temperature.

PRESSURE EFFECT: Figure 5 illustrates how pressure drop increases the tendency
of scale to form from saturated solutions. The pressure drop effect, coupled
with the decreasing solubility of gypsum at temperatures below + 100° F. ac-
counts for many of the crystal type scaling problems encountered in shallow,
low temperature reservoirs. Also the crystal scale development frequently en-
countered where pressure drop occurs in surface operations.

As shown by Figure 5 the rate of scaling increases with increasing pressure

drop. Once scaling has begun the fluid passages will plug rapidly. There have
been many instances where calcium sulfate scales have completely plugged
fluid passages. As shown in Figure 1, where such deposits occur in perfora-
tions or on the formation face the production will be markedly reduced.

DISSOLVED SALTS EFFECT: The solubility of calcium sulfate increases as the con-
tent of most of the soluble salts normally found in oil field waters increase.
Sodium chloride is usually the predominant salt and Figure 6 illustrates how
the solubility of calcium sulfate is markedly increased up to a salt concentra-
tion of 150 gms. per liter.

The variation in calcium sulfate solubility with salt content, when coupled with
the pressure effect can be a frequent cause of formation plugging in flood pro-
jects. When relatively fresh flood waters contact highly saline formation waters,
both of which are saturated with calcium sulfate, the salt concentration in the
mixture will be reduced. Under these conditions the solubility of calcium sulfate
will be exceeded and scale precipitation occurs. In most of the reservoir this
will not significantly reduce the permeability. But when it occurs in the well
bore zone or perforations and particularly when coupled with the pressure drop
effect, plugging can occur.

FACTORS EFFECTING WELL TREATING PROCEDURES (4)

Calcium scale removal treatments, being of the chemical conversion type, are time
dependent and there are a number of well bore conditions that will markedly
influence their effectiveness. The following factors should be evaluated where
the conventional "spot and wait" treatments are planned.

TREATING TIME: The conversion reaction whereby the calcium sulfate is changed to
a water or acid soluble compound is a surface active phenomena. This requires
maintaining intimate contact between the scale and the treating compound for a
significant period of time. Figure 7 illustrates that for optimum laboratory
conditions. With pea sized gravel crystals, a minimum of 6 hours is required for
100% conversion. In this test the total surface areas of the crystals were expos-
ed to 100% concentration of the treating compound. In well treatments the scale
would be attached to reservoir face or perforations and the reaction would be
occurring only over the exposed surface of the scale. Under these conditions the
time for conversion would be greatly increased. Field experience indicates that
in developing a procedure for a specific area or field, initial treatments
should be at least for a 24-hour period and preferably longer.

THIEF ZONES: In low pressure wells, where some strata are essentially depleted,
thief zones can markedly reduce treating effectiveness. Should the hydrostatic
head used in spotting the treatment be too high, most of the treating chemical
may enter the depleted strata. Where thief zones are known to exist a preflush
for partially filling the thief zone may be desirable. Also in the spotting of
the treatment every effort should be made to minimize the hydrostatic head.

WELL BORE WATER: As noted in Figure 3 concentration of the treating chemical is

of major importance, with a minimum concentration of 50% being considered neces-
sary. In most wells the producing zone will be filled with water and this may
extend up the hole. Also, if the scale is removed first from a high water pro-
ducing zone, there may be an inflow of water during the treatment. In determining
the concentration of the chemical the possibility of these extraneous waters
diluting the treatment must be considered. With open annulus spotting procedures
dual treatments may be required to obtain good results.

LOW PRESSURE ZONES: Where a highly depleted zone is plugged by scaling, once the
scale has been removed,there is the possibility of this acting as a thief zone.

FIELD TEST DATA: While field experience during the sixties had often been dis-
appointing, with the elimination of inadequate chemicals and the developing of
treating procedures the success ratio increased. The experiences in one West
Texas field for the period 1970 - 75 are shown in Table I (5). It is obvious
from this data, that where calcium sulfate scales are impairing production,
successful treatments are possible.

AN OPTIMUM WELL TREATING PROCEDURE (5)

As the problems associated with scale removal treatments discussed in the previ-
ous sections were discovered, procedures were developed to circumvent the diffi-
culties. The method described below, controls the hydrostatic head minimizing
the thief zone problem. In addition by isolating the zone to be treated, the
possibility of serious dilution of the chemical is prevented. Also by the use of
a controlled overflush, that squeezes treatment into the producing interval any
skin damage effect, due to scale, will be more directly treated.

The technique requires the use of packers and accessories. Careful control is
required with regard to-chemical volume and injection procedure. A programmed
well clean up is also required to assure maximum treating effectiveness. Obvi-
ously the method is far more expensive than the usual spotting method applied
in most treatments of this type. Prior to application well performance and
reservoir conditions should be reviewed. It is essential that the well have the
potential to produce significantly larger volumes of oil, to warrant the
additional cost of the treatment.

The increases in production that can be obtained with this type of treatment
are listed in Table II. These wells in a West Texas field were known to have
heavy gyp scale build-ups and with the increases shown, the additional expense
and time required for the optimum treatment was certainly justified.

TREATING EQUIPMENT AND PROCEDURE: The well equipment is illustrated in Figure 8.

It consists of a hook wall packer with a fluid spotting control valve, coupled to
the packer by a tail pipe, to position the valve close to the bottom of the zone
to be treated. The spring in the control valve is adjusted to the wells hydro-
static head, under closed in conditions. When the assembly has been run and the
slips set the treatment is pumped into the well. The recommended volume is 1-1/2
to 2 times that required to cover the zone to be treated. The chemical mixture is
displaced into the well with the volume of oil required to spot the treatment
over the zone to be treated. The packer is then set and the remaining volume of
chemical in the tubing is displaced into the formation.

The well is closed in for 24 hours, but preferably longer on initial treatments.
The well is returned to production, by swabbing the tubing dry, and dropping a
bar to shear the pin in the valve and open the block out sleeve. The swabbing
should be continued for two to four hours. This is to recover the residue of the
reaction and prevent any unconverted small crystals from being forced back into
the formation and acting as a nuclei for scale growth. The well should be
acidized for a final clean-up and stimulation.

CONCLUSIONS

1. Laboratory and field test programs have proved the calcium sulfate scales
can be successfully removed from the well bore face and perforations.

2. Marked increases in oil production can be obtained from reservoirs having

the potential for increased production.

3. Where large increases in production are possible the additional expenses

of optimum treatments are warranted.

4. Successful scale removal treatment should be followed by scale

inhibitor squeeze type treatments to minimize further scaling.

REFERENCES

(1) Mills R. : Van A. : The Paraffin Problems in Oil Wells, U.S. Bur.
Mines R. I. 2550 (1923)

(2) History of Petroleum Engineering, Pg. 598, American Petroleum Institute.

(3) NGSMA Handbook

(4) Richard S. Fulford, Effects of Brine Concentration and Pressure Drop

on Gypsum Scaling in Oil Wells, AIME SPE-1803, 1967

(5) Jerry N. Crane, An Engineered Approach For Successful Removal of

CaSO4 Scale Deposition; Petroleum Engineer, July 1972
 FIGURE CAPTIONS

Fig. 1. - Calcium Sulfate Scale Plugging And Clean Out

Results In A West Texas Well

Fig. 2. - Results With Gyp Scale Removal Chemicals

Fig. 3. - Average Effect Of Dilution On Gyp

Scale Removal Chemicals

Fig. 4. - Solubility Of Calcium Sulfate Scales In Water

Fig. 5. - Pressure Effect On Scaling Tendency Of

Calcium Sulfate

Fig. 6. - Effect Of Salt Concentration On Solubility Of

Calcium Sulfate
Fig. 7. - Rate Of Gyp Crystals Conversion Versus

Time Fig. 8. - Optimum Treating Procedure

Table I. - Gyp Scale Removal Treatdents In a West Texas Field

Table II.- Results With Optimum Well Treating Procedure

 inhibitor
senleeze
4000 --

1
0 ZL - TIAPPY.L.C/1101MI

3000

2000 _

1000 -1 I
1- CLEAN OUT PROGRAMS -i

62 I 63 I 64 1 65
__r ____
1 66 1 67
  .
"• "."."'"."••••,-4,.••

11.":4■••■'"
'•••"7"."

WEIGHT OF SAMPLE-11.45 grs.

TREATING EFFICIENCY —29%

TESTRESULTS

SAMPLE LOSS-4.71 gr
TREATED SAMPLE

ab i g p
.
.r■
C
E :E
0 Vb
FiVIURP1 - 2

GYP SCALE REMOVAL CHEMICALS

4
0
Li «C id,
" C•4a
E ". U a
0
0I .. 0 i n
W S
0••••
a ta V
.. to 0
*0
WEIGHT OF SAMPLE — 16.16

tu •
-.1 alat; "o
8.-
t-
ua
IL

Val

•••• t" *
la •IP •
0
-1.1 .0
14 : ...In 31 0
2 c .... t:t
V 0 E% 7:
 o
r... .., .0 4.0
k....2 — 3 0_
a c ;-,
E "v--t 0I a ...
a
.1
AVERAGE EFFECT OF DILUTION ON
GYP SCALE REMOVAL CHEMICALS
 i
i
Hot Water
i 15°/0 H
CI
 10 1111
0
—
80
Nr-

60
GYP SCALE CRYSTALS CONVERTED -%

40

20

0 100 50 25

10
CHEMICAL CONCENTRATION —%
 FInURT: - 4

S OLUB I LI TY OF SCALES IN WATER

ZOW
I
AtMI 1401Y
2400 DRATE
(C460.-
11/420
2200 )

2000
,GYPSUM
(CaS0.-
1100 2H20)

,
1600

i
1400

1111

Il
1200

100
ANwroar
0 ra
(Ca604
33 IS 104 140 171 212 240 214 120 36$
TEMPERATURE-'F
 SCALE PRECIPITATED

700 (6000 ppm in solution @ 100'F. & 100 gm/1 P4sCI)

z 600

2 see

7
loo200
3116

acio_________________________________

/tut 0 2

10 12 14 111
PRESSURE DROP in nein 100
 SOLUBILITY OF CALCIUM VS SALT CONCENTRATION

4000

z
0
n 5000

3
a
♦000 a

3000

2000
0 50 100 150
Gill Conaminition—ipme.11 IOW R
 GYP CRYSTALS CONVERSION
PERCENT VS TIME
(optimum for laboratory tests)

PERCENT CRYSTALS CONVERTED

 PACKER AND SPOTTING CONTROL VALVE
(unknown fluid level)

SLIPS SET
PACKER CLOSED
PACKER OPEN

BY-PASS
OPEN CLOSED

SPOTTING CHEMICAL

CHEMICAL ISOLATED

TAILPIPE

SPOTTING VALVE
OPEN CLOSED
 TABLE I
GYP SCALE REMOVAL TREATMENTS IN A
WEST TEXAS FIELD

BEFORE AFTER INCREASE

YEAR WELLS OIL WATER
10 17 OIL WATER OIL WATER
91 17 10 60 69 43 59
V 42 29 20 50 81 21 61
31 36 29 64 113 28 84
50 45 81 61 142 18 61
33 46 100 62 146 16 46
•
73TAL 17 23 110 35 175 12 65
rya 36 59 56 121 20 62
- 1 1
 TREATING RESULTS

Prior Production Production After

Well No. Oil Water Oil Water
1 12 0 197 46
2 7 3 37  37
3 21 8 120 102
4 8 21 31 393
5 17 13 61 56
6 44 0 89 97
7 35 9 81 68
8 61 5 96 31
9 8 13 72 104
10 37 16 96 35
Total 250 88 880 969