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Test Methods and Chemical Inhibition Practices 331

Makeup water \%;IS obtained from ;I municipal supply.
When desired, CLICI?or NaHCO, was added to the tap
woter. The water U;IS pre-heated to 40°C in the feed tanks
prior to entering the exchanger.
I n this system the CaSO, solution was maintained in a
saturated state by recirculating through a bed of gypsum
spheres and then through a fine filter prior to entering the
exchanger. The s!.stem was designed to be used for once-
through o r recirculation testing. Additional details on the
construction and operation of these apparati can be found in
the references cited.
Hasson et 31. later modified the feed water system of this
special test apparatus t o study the deposition mechanisms of
calcium sulfate scale. A schematic of this modified system is
shown i n Figure 8.28.
I n this system the CaSO, solution was maintained i n :I
saturated state by recirculating through a bed of g\psuni
spheres and then through a fine filter prior to entering the
exchanger. The system was designed t o be used for once-
through or recirculation testing. Additional details on the
const.ruction and operation of these apparati can be I'ound in
the references cited.
Electrodialysis Laboratory Deposit Test Unit
Berger and Lauriejh described a laboratory electrodialysis
unit used to study deposit problems and additive effec-
tiveness in the waste streams from such units. Their system
involved the 9 inch x 10 inch electrodialysis unit shown in
Figure 8.29. I n this unit alternating membranes, permeable

RETURN
LINE

DISTILLED WATER
, M MLUE-UP

RECYCLE
LINE

ROTAUETER 0
i
b
I
I 1 I

j
I

Figure 8.28. Modified double

(3 MAKE-UP
*
LINE t pipe heat exchanger scale
test apparatus. (After Hasson
MAKE-UP PUMP et al., 197035)

SALINE NATER OW PARTIALLY S A L I N E WATER TO DEMINERAL-

C O N C E N T R A T E D B R I N E TO CON- IZlNG COMPARTMENTS
:C12 OR OZGAS

TO POSITIVE W L E
TO NEGATIVE POLE

STEEL CATmxx

I I

t f 1
CATHOOE
WASTE
1
CONCENTRATED BRINE
i
PRODUCT
I
ANODE
WASTE
OR WASTE WATER
LEGEND
Figure 8.29. Electrodialysis C CATION M E M B R A N E @ ANY CATION (POSITIVE ION I L I K E SODIUM
deposit test unit. (After Berg- A ANION MEMBRANE
@) ANY A N I O N ( N E G A T I V E ION 1 L I K E CHLORIDE
er and Laurie, 1962.36)
332 Water-Formed Scale Deposits

DILUTE RECYCLE
only to cations or anions, a r e alternately stacked with _.

spacers between them. The spacers are arranged in a --1

manner that directs the stream flow and prevents back-
mixing. Turbulence promoters are used in the flow paths in
order to reduce or prevent concentration gradients. The
spacer arrangement also allows the concentrated waste
stream to be separated from the dilute product water
stream.
Figure 8.30 shows the “feed and bleed system” used with
the laboratory unit. It is arranged to allow the concentrated
waste stream to recycle continuously. It can also be used as WATER 8
A DDl TI V E S
a once-through system or to recycle the concentrate con- FOR COUC
tinuously but remove some concentrate (bleed) and add “FEED” “BLEED”
some feed water (feed) at such a rate that steady-state con-
ditions are achieved. Figure 8.30. Feed-bleed flowsheet for electrodialysis super-
Tests were made by placing additives (deposit inhibitors) saturation study. (After Berger and Laurie, 1962.36)
in the water that enters the concentrating stream. After tests
are completed the stack (membranes) is disassembled and
the location and amount of precipitate are noted.

Waterflood Core-Flow Studies

8 ig
There are numerous references in the literature concern-
ing the use of incompatible waters in waterflooding. Several
studies have been made to determine the effect of incom-
patible waters reacting in the formation, causing deposits
and subsequent plugging.

-
Bernard” made a laboratory study to determine the max-
imum amount of CaCO, supersaturation that can be carried
in an oilfield water without causing precipitation and
permeability reduction in a water injection well. The ap-
paratus for these “core flow” studies is shown in Figure
8.31. The core sections were 4 cm x 5 cin x 28-88 cm Berea LYAO*LIIC fT1RRER

sandstone cores, a uniform source of the sandstone cores

commonly used to study fluid flow in porous media in oil
Figure 8.31. Apparatus for determining effect of CaC03 -
supersaturation on formation permeability. (After Bernard,
and gas studies. The apparatus is designed to commingle 1957.37)
two incompatible fluids continuously and to control the flow
rates of the unstable solution through the test cores.
Permeability reduction was the measuring criterion.
Bernardj8 made another study of incompatible waters in-
volving the precipitation of barium sulfate in subsurface for-
mations. I n this case he used an apparatus similar to that
shown in Figure 8.32. A Berea sandstone core was saturated
with either a sodium sulfate o r barium chloride solution,
and the opposite solution was pumped through the core to
determine the permeability reduction due to precipitate for-
mation. Some of these data are discussed in Chapter 4. The
problem with such tests is that they only reflect what
happens in a uniform formation; they do not reflect the
severe scale problem that usually occurs in fractures and in
waterfloods when water breakthrough occurs in a producing
well and the fluids begin to commingle in the borehole.
( 0 \ 1 I I) ( O K 1
Complete scale cementation of downhole equipment has oc-
curred i n a s short as 21 days after water breakthrough oc-
curs. KIC 1 l \ l \ l r (1K\1)1 \I1 --
Scale inhibitor squeeze solutions can be tested in a similar
manner. Details of such procedures can be found in dis- Figure 8 32 Apparatus to determine formation plugging from
cussions hy Kerver and H e i l h e ~ k e r ’and
~ Vetter.40s41 scale precipitates. (After Bernard, 1957.38)
 Test Methods and Chemical Inhibition Practices
Miscellaneous
Tidball et al.42 described a method for detecting incipient
scaling i n seawater evaporators by measuring decreases in
heat transfer. Also included in their studies is a computer
program designed to plot heat transfer coefficients versus
hours on stream. K e r ~ treviewed
~~ several published
methods of evaluating coolicg tower water treatments and
proposed a tentative recommended practice based on this
review. DonohueJ4 provided a limited description of a por-
table monotube deposition tester used to test fouling rates in
cooling waters. A window in the apparatus allows visual
observation of fouling on a heated tube while temperature
differences are recorded automatically to quantitatively
define fouling rates.
Freedman et described a portable testing unit for
evaluating fouling and corrosion in cooling water systems.
This unit uses preweighed heated tubes along with corrosion
coupons enclosed in plastic blocks. Visual observations can
be made during operations and quantitative data can be ob-
t ained.
Field Monitoring Methods
The selection and use of scale inhibitors in actual plant
and field operations usually requires some type of monitor-
ing. Heat transfer coefficients, fluid flow measurements,
pressure drops, and plugging (increases in pressures) are
Figure 8.33. Typical perforated scale Coupons Inserted S o That Fluid Impingement
coupons used in petroleum industry. And Turbulence Occurs On Area O f Coupon
333
sometimes adequate indicants of solid or scale deposits; but
sometimes these occur too late to prevent a problem or shut
down.
Scale Coupons
Scale coupons are commonly used to provide more im-
mediate evidence of problems or to evaluate treatments in
certain types of operations such as those encountered i n the
petroleum industry. These coupons can vary from relatively
simple installations t o ones that can be inserted and pulled
hydraulically without closing the system down even though
it may be under high pressure and temperature.
A n example of one of the scale coupons used in petroleum
operations is shown in Figure 8.33. These coupons are made
out of 1020 carbon steel and are approximately %-inch
wide x 3 inches long x %-inch thick. Unlike corrosion test
coupons, they are perforated, and when placed in a fluid
stream, they are usually oriented in such a manner that the
the fluid flow actually impinges on the coupon, creating tur-
bulence. Scaling tendencies, if present, then accelerate. The
coupons are mounted on the special insulated chuck shown
in Figure 8.33. They are cleaned, weighed, inserted in the
system, exposed for the specified test time, dried, and
reweighed. The amount of scale deposited is recorded.
Changes in the system and the effectiveness of a treatment
can be measured in this manner.
334 Water-Formed Scale Deposits

Figure 8.34. Scale coupon

(0.75” x 3”) coated with
CaC03 in water disposal line
for 30 days, south Louisiana.
(Original perforations 0.25”
in diameter.)

4+ C o u p o n

1
/Post

Barrel

Barrel

r/

r i
1 9 a c k i n g Gland
-7
c: LJ
I

Figure 8.35. Extractable

scale coupon holder.
 Test Methods and Chemical Inhibition Practices
Figure 8.34 shows a scale coupon coated with calcium
carbonate. This coupon was exposed in a saltwater disposal
line for 30 days in south Louisiana. Figure 8.35 is a
schematic of a relatively inexpensive extractable coupon
holder. The coupons are attached to the holder and pulled
back into the barrel. T h e barrel is then screwed into a closed
valve (full-opening type). T h e valve is opened and the
coupon is inserted through it. An attachment between the
holder handle and the barrel holds the coupon in against the
system pressure. This device is often used in monitoring
scale deposition in once-through hot water heaters operating
at 450 psi and 320°F. Manual insertion of the coupons un-
der these conditions is difficult but possible. Higher
pressures require more elaborate hydraulic insertion
met hods.
Caliper Surweys in Oilwells
Caliper surveys a r e sometimes run in oilwells t o deter-
mine the presence and/or rate of growth of scale deposits.
These surveys are conducted by running a special tool
downhole on a wire liner. T h e tool has a series of spreading
fingers which measure the hole diameter continuously. T h e
results are transmitted electrically t o the surface, and
recordings are made of the hole diameter. If scale growth
occurs, a corresponding decrease in well diameter will oc-
cur. Scale deposition rates can be measured if logs are made
at different time intervals.
Figure 8.36. Test spool being removed from line to check CaC03 scale deposition in waterflood in south Texas.
335
Test Nipples or Spools
I n pipeline operations it is sometimes convenient to use
test nipples or spools to determine scale deposition. These
devices a r e small segments of pipe, either screwed o r
flanged, fitted into the line t o be tested. In some instances
the). a r e inserted in bypass loops like the one s h o u n in
Figure 8.36. In this type of installation the nipple or spool
can be removed by closing the bypass loop without shutting
the system in. Scale deposition can be measured visuall!, by
weight (usually by scrapings. since the test section weighs
far more than the scale deposit) or by deposit thickness (in-
crease or decrease).
Differential Thermocouples
Differential thermocouple measurements are used to
measure both location and rate of scale deposition in once-
through high-pressure industrial water heaters. In these in-
stances one set of thermocouples is installed at varying
points on the outside of the tubes in the firebox and a second
set is placed in the water in the tubes. I t % a s f o u n d that
e-
s c a I f r ee t u be s m a i n t a i n ed a constant d i f fe r e ri t i :i 1 .s.
, ;i I e
scI
is deposited the bulk water temperature decreases slightly,
and the firebox thermocouples show a significant rise i n
temperature with scale thickness and location. Alarm
systems and a n automatic shutdown mechanism are built-in
and will go off if the outside metal temperature in the
firebox reaches a preset limit.
i B y - pass Loop
336 Water-Formed Scale Deposits

Precipitate
8.5

-
I,
m
C
-uJ
and Inhibitor
$ 8.0

$1
No Inhibitor

7.5 Incremental NaOH Addition 4

0 2 4 6 8 10 12 14 16 18 20 Figure 8.38. Effect on pH of cooling water of incremental ad-

Incremental NaOH Addition
ditions of NaOH. (After Feitler, 1972.4s,47)

Figure 8.37. Critical pH as determined by addition of NaOH

and plotting resultant pH in cooling water. (After Feitler,
1972.4s*47)

Constant
Head
Reagent
Material Balances Container

Water analyses can sometimes be used to determine

material balance calculations where scale deposition is ex-
pected. Calcium analyses, for example, taken in and out of a
steam generator or a heater treater can sometimes be used
to determine whether or not scale is depositing to any major
extent. It is usually necessary, however, to run a full water
analysis on both inlet and outlet waters. Another ion, such
as chloride, known not to deposit should be used as a base Outlet
line so that errors, evaporation or sampling, etc. can be Drain
taken into account.

The Use of Scale Meters

in Cooling Water Control

Feitler46.47describes a method for determining, monitor-

ing, and measuring the “critical pH” (pHc), or the “true pH
of scaling of cooling waters.” He indicates that the critical
pH is 1.7 to 2.0 units higher than the pH of saturation in-
dicated by the conventional Saturation Index. The basis in
theory for this critical pH measurement is the unusual
decrease in pH (at a certain point) of a calcium carbonate-
containing water (untreated) with increasing additions of a
caustic. The critical pH is determined by titrating a water
with increments of NaOH and then plotting the pH shown
in Figure 8.37 (untreated water). The point on the extension Water Out
of the curve just after the maximum pH is the critical pH. Figure 8.39. Flow diagram of scale meter. (After Feitler,
If precipitation (potential scaling) does not occur the pH 1972.46947)
continues to increase with increase in NaOH. Figure 8.38
shows examples of a water which has been treated to prevent
precipitation (Curve l), the same water with no treatment
(Curve 2), and the same water with a normal amount of
scale inhibitor added. measurements. Figure 8.39 shows a flow diagram of the
The scale meter is designed for use in cooling waters and scale meter. A water sample is passed through a constant
takes into account the factors dealing with critical pH flow module (100 ml/min or 2 gph). The water is then sent
 Test Methods and Chemical Inhibition Practices 337

to a mixing tee where it is treated with N a O H . Precipitates
of C a C 0 3 form and are allowed time to grow (90 sec) to
detectable size with a time-delay tube. A special photometer
affords particle measurement. The signal from the photocell
is amplified and is used to actuate the control and alarm cir-
cuits. The water sample flows to waste over a special weir.
A total dissolved solids monitor is an integral part of the
scale meter. This unit is based on electrical conductivity and
is used to control the cycles of concentration.
Figure 8.40 shows a method of using the scale meter on a
cooling tower installation. The water sample is taken from
the return line to the cooling tower. The total dissolved
solids are measured and a control valve is actuated to blow-
down the system automatically and to introduce fresh
make-up water to control the solids. Concentration cycles
are thus controlled automatically to predetermined limits.
The scale meter control signal is tied into a scale inhibitor
pump which adds inhibitor as needed, based on critical p H ,
to keep the system from scaling. Alarms are sounded if
either the photolamp in the scale meter or the inhibitor feed
system fails.

Monitoring and Controlling Cooling Waters. Numer-

ous instruments are available for controlling and monitor-
Water Sample I I ing cooling waters. Some equipment is elaborate and some
Return relatively simple. Poole and Bacon4* reviewed the present
Scale methods of monitoring and controlling cooling water
Valve Scale
treatments. Table 8.6 summarizes their findings.
Meter

Ultrasonic Scale Detection

' land Storage- I II 1 Instrument
1 Basin
Cooling Tower Bleed
7 9
TDS Lonrrt
i- -r
Power
Methods of detecting the rate of scale deposition while a
process stream or piece of equipment is in operation are
often useful. Midwest Research Institute49developed such a
Valve Scale Alarm 9 ? r;?
$ ~ Power method based on ultrasonic reflectivity changes at liq-
uid/metal interfaces. Small high-temperature transducers
m
3
+
are soldered directly to the outside of heat transfer tubes.
The geometry is such that the echo trains produced by the
Figure 8.40. Typical installation for a scale inhibitor chemical device are stable at water temperatures up to 280°F and
treatment program control system. (After Feitler, 1972.46-47) flow velocities of 3 ft/sec. The sensitivity increases with in-

Treatment Program Monitoring Measurements Treatment Program Monitoring Measurements

Scale Prevention Control of Biological Fouling

Control concentration b y bleed
from system
Lower Saturation Index b y
feeding acid
"Threshold" polyphosphate
Organic phosphorous compounds
Crystal-distorting polymers
Corrosion Inhibition
Adjust Saturation Index t o produce
a controlled calcium carbonate
scale (feed lime or caustic)
Chromates (200-1000 ppm)
Chromate-phosphate (60 ?r ppm)
Organic chromates
ZincahosDhate
~ I .
Modified tannins and carbo-
hydrates + zinc
Synthetic polymers with film-
forming functional groups
Phosphonium compounds
~
A Specific conductivity or Chlorination-liquid chlorine A Colorimetric (orthotolidine)
chloride ratios or hypochlorite Amperometric
A Calcium hardness, alkalinity, Potentiometric ( O R P I
total solids and pH Chlorine donors (phenates, etc. No test
Total and inverted PO4 non-oxidizing)
No test' Quaternary ammonium compounds Colorimetric oi ti tr imetr ic
No test Copper salts Test not used'
Thiocyanates Test not used'
Acrolei n Colorimetric
Calci u m hardness, a Ika Ii ni t y ,
total solids and pH
A Colorimetric C r 0 4 Control of Nonbiological Fouling
A Total and inverted PO4 Side-stream filtration Turbidity
A Notest.' Dispersant or flocculating Heat transfer measurement
A Colorimetric Zn I antifoulants
A Colorimetric Zn
*Small pilot heat exchangers are used to follow scale deposition when water
quality control by chemical testing is not used.
A No t e s t * * * * T h e depolarization current corresponding to a fixed voltage drop across
electrodes i s used t o meter corrosion rate and pitting in the lnterloc and
A No test** Magna instruments.

After Poole and Bacon, 1972.48

338 Water-Formed Scale Deposits

creased frequency, but attenuation by the water establishes
an upper practical limit.
The decay rate produced by the device is highly dependent
on the nature of the scale, but the unit is capable of detecting
film deposits above 1 mil.
Fouling tests, both process side and waterside, are
reported in several ways: fouling factor calculations,
changes in heat transfer coefficient, pressure differentials,
temperature differentials, and also on a simple weight basis
or percent protection as compared to an untreated system.

Boiler Water Sampling Device Process Side Antifoulant Test Equipment

The use of antifoulants in process side operations is a

In determining the conditions occurring inside a boiler, it
is sometimes necessary to sample water for analysis on the
downstream or high-temperature side of the boiler. Special
sampling devices are needed to prevent flashing. Figure 8.41
shows an example of two devices, one for high-temperature
and high-pressure sampling and one for low pressure. Both
devices provide a means of cooling and collecting hot water
samples.
Test Results
Laboratory test results on scale deposits are commonly
reported on a simple weight basis when treated or inhibited
samples are compared with untreated samples. I n other
cases a “percent protection” is noted. This is determined as
follows:
‘h Scaling l’iotection =
I .OO W t o I Scale x 100
W t . o f Scdle o f Avg. Blank
(w1 t Iiou t inhi t) it o r )
relatively new area and little literature is available on the
subject. The fouling deposits, however, do create the same
loss in heat transfer efficiency as waterside deposits, so the
subject of process side fouling is relevant to any discussion
on scale deposits.
Various equipment is used to evaluate process side fouling
and antifoulants, particularly in refinery and petrochemical
operations. Some tests provide only qualitative screening
data. An example of such a test is the “hot-wire fouling
test.” In this test a low-voltage current is applied to high-
resistance wires placed in a hydrocarbon process stream.
When the temperature is increased sufficiently, foulants will
accumulate on the hot wire. Tests are normally run for
periods of 6 to 24 hours. Visual observations of foulant ac-
cumulation are used as test criteria. Antifoulants can be
screened for their effectiveness by the same procedures.
Figure 8.42 is a schematic of this unit.
The Erdco Coker in Figure 8.43 is frequently used to
evaluate the coking tendencies of jet fuels as well as the
effectiveness of antifoulants in other nonaqueous process
streams. This antifoulant device was first described in
1965.50 Fouling tests using this device are similar to the Erd-
co Aviation Fuel Testing Procedure, ASTM D- 1660. In this

Copper Coils

( a ) High Pressure

Figure 8.41. Special boiler water sampling devices. (From Standard Methods for the Examination of Water and Wastewater,
American Public Health Assoc., Inc., N.Y., 1967, p. 49.)
 Test Methods and Chemical Inhibition Practices 339

test, samples of fuel (sometimes deliberately aerated) are Pressure drop, in. Hg (logarithmic scale)
preheated to 204°C (400°F) and then passed across a stan-
dardized porous metal filter held a t 260°C (500°F) and into
a weighed sample receiver. The pressure drop across the
filter is recorded as a function of time.
Pressures drop exponentially with time as shown in
Figure 8.44a. The upper curve is typical of a high-fouling
feed stock where the pressure drops rapidly in a short period
of time. The lower curve indicates relatively slight pressure
drops over a period of time. This is typical of low-fouling
stocks.
One expression of fouling tendencies is the ratio of the
test slope to the slope of a low-fouling-tendency stock. This
ratio is referred to as thefouling index. Figure 8.44b shows
how to calculate this index.
>.I!
tx*
" "
'0
' "
:[
' "
-,1
"
i
"

,
'
,
. '
I
'
I"
' . "
,': ,
"
'1813
Length of test, minutes

Figure 8.44a. Pressure drop across porous metal filter as a

measure of fouling. (After Frazier et al., 196!f1.~O)

Fouling slope
Fouling index = --------
0.0035
Fouling slope = As defined in Fig. 8.44b
0.0035 = fouling slope of reference heavy virgin naphtha

1
Time
Figure 8.42. Hot wire fouling test. (From "Simple Device Tests Figure 8.44b. Calculating the fouling index. (After Frazier et
for Antifoulants," Oil and Gas J., Feb. 3, 1969.) al., 1 9 6 5 ~ ~ ~ )

oler

Figure 8.43. Schematic

diagram of Erdco* Coker
used t o evaluate fouling
tendencies and antifoulants.
( * T r a d e n a m e of E r d c o
Engineering Corp., Addison,
Receiver and scale Ill. A f t e r Frazier et al.,
1965.50)
340 Water-Formed Scale Deposits

The fouling index is a reasonably reliable indicator of Table 8.7. Determination of Optimum Concentration of
fouling tendencies as well as a method of selecting and Antifoulant by Use of Fouling Index
applying antifoulants. Table 8.7 illustrates how fouling in-
dex data can be used to select the optimum antifoulant. Additive concentration, ppm Fouling index
Preheater tube deposits are also examined. The entire
40.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
system operates at 150 psig. The principle limitation of this 20, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
test is that it requires large samples and as much as a week 10. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2
to complete a single test. 0. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.9
Another version of this test is shown in Figure 8.45. This
After Frazier et al., 1965.5O
test operates on an essentially closed system where the sam-
ple is pressurized across an annular heater, cooled, and
collected as waste. The fouling in the heater is noted.
Still another method of testing antifoulants in the vapor
phase is shown in Figure 8.46. The fouling tendencies or
selection of antifoulants are based on the decrease in sample
outlet temperature and the condition of the heater tube after Reservoir Outlet
a specified period of time. Inlet
S o m e investigators consider additive performance
screened on the standard coker used to evaluate the thermal
stability of jet fuels unsatisfactory for refinery process side
fouling studies. This is because refinery conditions are not
adequately duplicated. Fluid velocity, residence time,
temperature, pressure and metallurgy are generally quite
different from refinery operations.
Canaparys’ used the apparatus shown in Figure 8.47 to Temperature
Bath
u
E f f l u e n t Can
study process side fouling. The hydrocarbon stream is
pumped through an electrically-heated tube. Heat transfer Pressure Range __ 100.700 psig
coefficients are measured by taking temperature readings of Temperature Range -200-700 F
the wall surface and the oil. The average operating con- Charge Rate @ 4iilhr
ditions for this unit are noted (see Figure 8.47). Velocity @ 112 f t l s e c
GillespieS2described an improved antifoulant test based Figure 8.45. Laboratory fouling apparatus used to select an-
on the use of the Jet Fuel Thermal Oxidation Tester tifoulants, based on measurements of the decreased
(JFTOT). This device operates on the same general prin- temperature due to build-up foulants. (After NACE, 1970.153)
ciples as the Erdco Coker. Figure 8.48 is a schematic of it.
The reservoir is smaller than the Erdco Coker, using only 1
quart instead of 5 gallons of sample. The preheater tube is
63/8 inches long and has a test section %-inch OD x 23/x-
inches. It can be made of aluminum or stainless if test
temperatures are to exceed 343°C (650°F). Temperatures

Ii
are measured by a movable thermocouple inside the tube.
The J F T O T test is run for 300 minutes (when possible) and J-. L
the change in pressure is plotted as a function of time. P
-P
Figure 8.49 shows some typical antifoulant evaluation data.
These data are plotted to indicate the least fouling with
minimum line slope.
Other test devices for foulant measurement and an-
tifoulant evaluations include hot probes where deposits are
removed and weighed;s3 high-surface area stainless steel Waste
packed columns measured for deposit formation;54devices
for measuring changes in heat transfer coefficients with Feed
time;” and zeta potential and electrical conductivity
techniques.’h*!’ Cooler
recently discussed a new antifoulant test
suitable for use in the laboratory or as a side stream test unit
in a refinery. The test is based on a modification of the hot
wire technique and can be used to determine heat transfer
coefficients under a wide range of temperature conditions.
The hot wire technique involves placing an electrically
Y 1
heated wire inside a beaker of hydrocarbon. Hausler’s
Figure 8.46. Liquid-vapor phase fouling apparatus. (After
i Te.ut rcintinurd on page 3421 NACE, 1970.’53)
 Test Methods and Chemical Inhibition Practices 341

Safety
Switch

Refinery Stream Fouling Apparatus, Typical Operating

Conditions Oil Flow -Wall
............................ Naptha, gas, oil, crude. residue
(gal/hr) . . . . . . . . . . . . . . . . . . . . 1-2
Velocity (ft/sec) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-8
Average resistance time (min) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Pressure (psig) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , , , 150-750
Heated area (sq I"). . . . . . . . . . . . . . . . . . . . . . . , , ..0.16
Heat input ( B t u / h r ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,3000-5200
Tube-uall temp. ( O F ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , , 500- 1000
Heat transfer (Btu/hr/ft:) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19,000-33,000
Oil temp. ( O F ) . . . . . . . . . . . . . . . . . . . . . . . .300-600
Heat trans. coefficient iple
( Bt u / h r/ f't / F) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40-300
Tube cross-section shows construction details and how the
thermocouple connects to the tube.

Figure 8.47. Nalco refinery stream fouling apparatus. (After Canapary, 1961 . 5 1 )

25
METERING PUMP
CONST. S P E E D COOLER
C R U D E . TAR
>
X

t i)
w
Q:

I
Ln CRUDE ALONE
w
'ER I
z
-
U

FUEL RESERVOIR
w/PISTON & V E E - S E
-- % 0.

FRESH FUEL FILTER 0 100 200 300

T E S T TIME - MINUTES
Figure 8.48. Fuel system schematic of JFTOT Coker' used in
antifoulant testing. (*Tradename of Alcor, Inc., San Antonio, Figure 8.49. Comparative laboratory JFTOT Coker tests on
Texas. After Gillespie, 1971 .52) heavy stock. (Modified after Gillespie, 1971 .52)
342 Water-Formed Scale Deposits

(continuedfrom page 340)

modification of this test involves placing the hot wire in a
0.25-inch diameter tube so that the hydrocarbon stream can
flow over it. Two cross connectors are tied together by 2 in-
ches of stainless steel tubing. The electrical probe wire is
then placed inside the tubing. Electrical connectors extend
outside the unit to a power source. One opening in each
cross connector contains a thermocouple to measure inlet
and outlet temperatures of the hydrocarbon stream. The
other opening in each connector is the inlet and outlet for
hydrocarbon flow (see Figure 8.50).
Tests are run by pumping hydrocarbon from a 1-gallon
reservoir, through a preheater, into the probe where it con-
tacts the hot-wire surface, out of the probe, into a cooler
(immediately returned to room temperature) and returned
to the reservoir. The temperature of the wire and the feed
stream and the flow rate of the hydrocarbon stream are the
three controlling parameters. Since fouling rates are a func-
tion of temperature, a nonuniform deposit is noted on the
wire. This is caused by the increase in hydrocarbon and wire
temperature in the direction of flow as the fluid moves the
probe. Film transfer coefficients (heat transfer coefficients
from wire to liquid) are used as terms to report the results of
fouling tendencies. Plotting heat transfer coefficients as a
function of time gives an indication of the fouling rates.
Figure 8.51 illustrates the fouling effects determined by
the U O P Fouling Probe on six different skin-fluid
temperature variations on a reference diesel fuel containing
no additives. A rapid drop in heat transfer efficiency is
shown to occur at mild conditions in a relatively short
period of time.
There are numerous difficulties in testing and evaluating
fouling tendencies of hydrocarbon and antifoulants. The
nature of the deposit can significantly influence the heat
transfer coefficient. Simple weighing of deposits is not
necessarily related to the heat transfer coefficient or rate of
fouling.”
Antifoulants found to be effective at one temperature
may not necessarily be effective at other temperatures.
Thus, antifoulants tested a t one temperature under
laboratory conditions mayt not be effective over the wide
range of temperatures encountered in field operations.
Another difficulty in most fouling studies made by tubular
heat exchangers is that fouling rates represent the average
for the entire heat exchanger. Such data d o not always
reflect the rate at which a deposit can build up in a certain
area.
Although weight measurements and visual observations
are useful for determining the morphology of the deposits,
they contribute little to measuring the kinetics of the fouling
process. Therefore, the heat transfer coefficient or film
transfer coefficient should be used as the measuring
parameter in fouling studies. Visual inspection of equip-
ment, although not often possible until problems occur, is
the only sure method of deposit monitoring. All other
methods usually provide indirect evidence only. In some
pilot operations, tubes are removed from tube bundles for
inspection.hn
I n actual plant operations process side antifoulants are Figure 8.50. UOP process side fouling probe test unit. (After
evaluated on factors such as throughput rates, run lengths, Hausler, 1973.58)
 Test Methods and Chemical Inhibition Practices
*Hot-wire probe, Temp., "(.
TI, = Fluid temperature
1, = Probe temperature
10 20 30 40
Tim, hr
heat transfer coefficients, pressure drops, fuel consumption,
steam consumption, and conditions of special coupon ex-
posure. Plant tests on antifoulants are usually long-term,
and meaningful evaluations may take from 3 to 40 months.
The only conclusive test for a potential antifoulant is a plant
trial which is costly and time-consuming, and this is the
reason that pertinent and meaningful laboratory tests are
essential for evaluating fouling problems and process side
anti foulants.
Most laboratory tests on scale and deposit inhibitors can-
not be translated directly into results in field operations,
regardless of how accurate the tests are. This makes the
evaluation and selection of such deposit control additives
extremely difficult. Reliable field monitoring procedures are
equally difficult due to the complex nature of both the
system and the deposit. New laboratory and field test
methods are developed constantly in order to improve on
the development, evaluation, selection, and application of
deposit control additives.
One last observation concerning the research, develop-
ment, application, and ultimate evaluation of scale in-
hibitors, antifoulants, and other deposit control agents or
techniques-in most instances there are no standard tests.
Therefore, chemical additive suppliers or consulting
engineering services are sometimes confronted with the
problem of providing products or services for individual
company testing techniques only. Consequently, what may
be suitable for one company can be wholly inadequate for
another. This accounts, in part, for the large number of
chemical additives being marketed as deposit inhibitors to-
day.
Current Chemical Inhibition Practices
The chemical inhibition of scale and other deposits varies
in technique and, sometimes, in types of chemicals not just
between industries but even within the same industry.
Furthermore, new developments in technology, chemicals,
and operating equipment make for rapid changes. Thus, it is
not possible to cover all practices in detail. Two key in-
dustries, the petroleum industry and the saline water conver-
343
Figye 8.51. Diesel fuel foul-
50 do ' 70 '
ing using UOP fouling probe.
(After Hausler, 1973.5*)
sion industry, have been selected for detailed discussion, as
have the two major water usage areas, heating and cooling.
This overview should provide some insight into current
chemical methods for scale and deposit inhibition.
The Scale Problem
in the Petroleum Industry
Very frequently, the results of tests on completed oil and
gas wells show good production potentials. Immediately
after being put on stream or at sometime during their
productive life a decline in production occurs and no ap-
parent or ready explanation exists, though there might be
many reasons. More often than not, one of the problems is
mineral scale in the form of calcium carbonate, barium sul-
fate or calcium sulfate deposits occurring at some point in
the producing system and restricting the flow of production.
This deposition can occur at any point from the time the
produced fluids, which always contain water with dissolved
mineral matter, begin to move along minute fractures into
larger fractures and eventually into the well bore, through a
pump (where this exists), up the tubing string, through
valves, through surface separation equipment, into gather-
ing lines, and are diverted either into transmission lines on
the way to a refinery or to a gathering system, either to be
disposed or reinjected for waterflooding. At any point in this
route the minerals have ample opportunity to come out of
solution and deposit.
These deposits can sometimes be dissolved with acids
(predominantly carbonate-based scales) or disintegrated
(some sulfate-type scales). Where barium sulfate occurs,
and this is rather common, equipment sometimes must be
discarded or mechanical clean-out techniques have to be
used. No known chemical methods are effective in removing
a predominantly BaS04scale deposit.
The problem with treating producing wells in the oilfield
is that there is little opportunity to treat the water before it
begins to become unstable back in the formation. Further-
more, treatments must deal with a wide variety of natural
brines that vary more in chemical constituents than most
344 Water-Formed Scale Deposits
surface waters do. Pressures and temperatures are con-
siderably more variable than those in plant operations.
Also, one is usually working rather blind, since the problem
may be some 20,000 feet or deeper and in a very restricted
area of usually less than 6-inch diameter holes.
Water is both a problem and a valuable resource to the
petroleum industry. It exists as connate brines in hydrocar-
bon reservoirs and is produced in varying but large quan-
tities with almost all oil and gas. Since it is a subsurface
brine, water becomes highly mineralized by its contact with
formation rock coupled with high pressures and
temperatures and, in some cases, bacterial activity over long
periods of geologic time.
These waters change constantly with time, although the
changes may be so minute that the waters are considered to
be in an equilibrium condition. Once the formation is
tapped with a drill, however, and the formation fluids are
brought to the surface, the water undergoes rapid and
drastic changes. As stated previously, the water changes
continuously during the production cycle, and can dissolve
or deposit solids or other matter with which it comes in con-
tact. The oil industry has been plagued with a severe scale
problem (only one of the problems with water) since its
beginning. However, it has also required large volumes of
water in recovery and processing operations. What then are
the current practices used to control or prevent scale
problems in petroleum operations? What are the types of
chemicals used? How are they used, and what is expected of
them in terms of performance? These are questions to which
this section is addressed.
What Has Been Done to Resolve the Scale Problem?
Many papers have been written on the subject of scale in-
hibition in oilfield operations. It would be impossible to in-
clude all of the publications that have mentioned the scale
problem in relation to oilfield operations, but a brief review
of some of the more pertinent papers should provide a
reasonable base for any further research on specific details.
The early treatment for scale in the petroleum industry
generally paralleled the use of scale inhibitors in municipal
waters, boiler waters, and cooling waters. Krynine61 and
Yuster62 discussed the scale problem in waterflood
operations as early as 1938 and 1939. Acid salts and
phosphates were suggested as possible chemical treatments,
apparently because of the early successes of sodium hex-
ametaphosphates as scale inhibitors in other types of in-
dustrial water treating. In 1943 Battle and JesserP
described one of the first uses of sodium hex-
ametaphosphate for brine stabilization in oilfield waterflood
operations. In 1951 Kleber64 detailed the use of sodium hex-
ametaphosphate in treating scale deposition in primary
producing wells, waterfloods, and brine disposal systems.
Theory, method of treatment, and several case histories
were described.
Stiff and Davis65,66developed empirical methods for
predicting the solubility of calcium carbonate and calcium
sulfate in natural brines (1951-1952). Some experimental
deviations from predicted CaS04 solubility were later
observed by these authors and other investigators, and even-
tually this early CaS04 predictive technique was proven
inadequate and was modified.
In 1954 B u r ~ i kstudied
~~ the inhibition of gypsum
precipitation by sodium polyphosphates and described the
reversion characteristics as related to the effectiveness of
various types of polyphosphates. Crawford68 wrote a series
of short articles describing various aspects of the scale and
scale inhibitor problem as related to oilfield waters (1957-
1963). He also presented an overview of sequestrants and
chelation as applied to oilfield brines.
Earlougher and reported one of the earliest uses of
fracturing solid controlled-solubility phosphates back into a
formation in order to obtain slow feedback to prevent scale
deposits in the formation and downhole equipment of
producing wells (1957).
In 1959 Featherston et al.70described the characteristics
to be considered when selecting di-metallic phosphates (con-
trolled solubility) for injecting into producing zones in con-
junction with oilfield fracturing operations. Field results
utilizing the slowly-soluble phosphates were described.
Characteristics such as solution rate, particle size, reversion
rate, and re-precipitation problems were noted.
Featherston71 also reported on the removal and prevention
of scale in producing oil wells (1959).
Sloat72y73discussed in detail the proper use of controlled-
solubility phosphates as scale inhibitors in oilfield produc-
tion operations. Basic treating methods such as well pack-
ing, filter packing, and monitoring technique were detailed
(1963 and 1964). The effect of solution rate parameters was
also described. In 1963 OstrofT4 discussed a method of
calculating the amount of scale formed in injection wells as
a result of excess constituents that form deposits in water
systems in oilfield brines. Stone et al.75 reported on the
development of a Laboratory Scale Deposition Test Cell
used to study scale deposition mechanisms and scale in-
hibitors under simulated once-through petroleum producing
operations (1964). Several types of test instruments have
been built around this concept since this earlier work.
For those interested in some typical water handling
problems in the reinjection of large volumes of produced
water in secondary operations, a review of Dixon and New-
ton'sT6 study will be valuable. They studied several water in-
jection projects. These included both open and closed
systems where injection volumes varied from 2,200 to
12,500 barrels per day. The projects included both limestone
and sand formations varying in depth from 1,300 to 6,750
feet with permeabilities of 17 to 275 md. (1965).
Gates and C a r a ~ a discussed
y ~ ~ ~ ~the~ extensive problem
of barium sulfate scale deposits in producing wells in
California (1965). Slaton et a1.79,80described scale deposi-
tion and removal problems as related to oilfield operations
(1965). Metler and Ostroffsl derived formulas for predicting
the solubility of calcium sulfate in various electrolytes en-
countered in natural brines at temperatures from 28" to
70°C (1967). Tate et a1.82showed that the original Stiff and
Davis procedure for predicting calcium sulfate solubility in
oilfield waters was inaccurate (1964).
Stone83 discussed the use of organophosphonate
derivatives in removing and preventing calcium sulfate scale
 Test Methods and Chemical Inhibition Practices
deposition in wells in the west Texas area. He discussed the
scale inhibitor squeeze technique and the field results ob-
tained (1966).
Collins and Zelinskis4determined the solubility of barium
sulfate and strontium sulfate in oilfield brines (1966).
Tinsley et al.85 discussed the design of chemical fracture
squeeze treatments of oil wells in order to prevent scale
deposition (1967). Bradleys6 investigated the use of series*
sodium ion exchangers to soften water for steam production
in steamflood operations (1967). Weintritt and Cowap87 dis-
cussed the unique characteristics of barium sulfate scale
deposited from subsurface waters, and the effect of in-
hibitors on this type of scale (1967). TempletonsS derived
methods for predicting the solubility of barium sulfate in
natural brines at temperatures from 25OC to 95OC (1960).
Hulls9 reported on a process that internally softens and
makes high-pressure steam directly from hard saline waters
or other brines. Claims are that scale is eliminated on
process heating surfaces (1967). HigginsgOdescribed a con-
tinuous ion exchange method for treating water to eliminate
scale in high-pressure steam generators used in oilfield ther-
mal flood operations (1967).
Jonesg1described a new laboratory scale test apparatus
for use in oilfield brine studies. He used the test apparatus to
study the effect of various chemical additives on inhibiting
the formation of calcium sulfate and calcium carbonate
(1961).
OstrofP2 published an excellent book entitled Zntroduc-
tion to Oilfield Water Technology in 1965. An entire
chapter is devoted to the problem of scale deposition in
oilfield operations. Diebes and Jesseng3 presented
laboratory data on a new laboratory test device for studying
the effect of scale deposition and scale inhibitors in oilfield
brines. Their study involved calcium carbonate deposits
from natural brines (1967). This paper contains an excellent
bibliography related to calcium carbonate scale.
Smith et a1.94 presented the results of a laboratory and
field testing program that involved the use of scale inhibitors
and removal agents on calcium sulfate scale found in
waterflood projects (1968). Carlberg and Casad95 made
laboratory studies to determine the effect of various scale
inhibitors suitable for producing steam for thermal flood
operations (1967). Larseng6detailed some new methods for
treating surface and subsurface waters used in oilfield
operations. Particular emphasis is placed on removal of
suspended and dissolved solids in order to prevent scale
deposits (1967).
Martin9’ discussed the possible causes of supersaturation
and deposition of calcium sulfate from oilfield brines, and
how these might be predicted (1967). Lasater et al.98
described the effect of various types of inhibitors on oilfield
calcium carbonate and calcium sulfate scale deposits. The
inhibitors included polyorganic acids, organic phosphates,
inorganic phosphates, and other chelating agents (1968).
Templeton and Rogersg9described methods to predict the
solubility of anhydrite in hot water or steam droplets for
saturated steam pressures as high as 2,000 psig (637°F).
These data were developed for use in predicting scaling
tendencies in natural waters used for generating wet steam
in thermal oil recovery operations (1968).
345
Kerver and HeilheckerioOmade extensive laboratory and
field tests on various scale inhibitors used in squeeze
treatments of oil wells. Calcium sulfate scale was of prime
interest in this study. Adsorption-desorption characteristics
were measured on field cores, and the results of extensive
field tests were discussed (1968).
Bilhartzlol discussed the importance of a standard data
.acquisition method for monitoring injection water quality.
He placed particular emphasis on data related to suspended
and dissolved solids that cause scale deposits and formation
plugging (1968). Fulfordlo2 discussed the effects of brine
concentration and pressure drops on gypsum scaling in oil
wells. This was one of the early investigations that noted the
important effect of pressure on the deposition of calcium
sulfate scale (1968).
Skillman et al.1°3 described a method for calculating the
solubility of calcium sulfate in oilfield brines based on ther-
modynamic solubility theory. Temperature ranges and salt
concentrations normal to oilfield operattiom were covered,
and time-sharing computer services utilizing calculation
routines were discussed (1969).
Dowling”J4 discussed the use of an organophosphonate
scale inhibitor in a waterflood operation in New Mexico
(1969). Vetterlo5 critiqued test methods used to evaluate
oilfield scale inhibitors. He noted that several types of tests
should be run. The effectiveness of polyelectrolytes,
phosphate esters, and phosphonates were studied in relation
to barium sulfate, calcium sulfate, and calcium carbonate
scale inhibition (1970). Vetter and Phillipsioa compared
methods of predicting calcium sulfate scale under downhole
well conditions. They noted the inconsistencies and
limitations of other prediction methods, particularly in
regards to pressure effects. They proposed a new method of
prediction based on thermodynamic relations (1969).
Ralstonl07 discussed the effect of aminomethylenephos-
phonates on calcium carbonate, calcium sulfate, and barium
sulfate scale deposits commonly found in oilfield operations
(1969). Bezemer and BauerloSreported on methods used to
design controlled-solubility well packs in order to prevent
calcium carbonate scale in wells in South Sumatran oilfields
in Indonesia (1969). Park et al.109 discussed a combination
scale, corrosion, and emulsion treatment based on squeeze
techniques and used to prevent barium sulfate and calcium
carbonate scale in oil and gas wells (1969). CowaniIodis-
cussed the secondary properties necessary in chemicals used
for mineral scale inhibition in the oil industry (1970).
Case”l published an excellent operator’s manual entitled
Water Problems in Oil Production, 1970. This book has
some practical solutions concerning solid deposits, scale for-
mation, and plugging and fouling deposits in oilfield waters.
An entire chapter is devoted to the subject of scale-control
“gadgets” in the oil industry. Case is recognized as an
authority on water-related deposit problems in oil
operations. He has published numerous articles related to
solids deposits from oilfield waters.112~113~i14~1i5
Davis and Collins116 studied the solubility of barium and
strontium sulfate in strong electrolyte solutions as an exten-
sion of their earlier work related to oilfield scale deposits
(197 1). Vetterll7*11*discussed radioactive tracer techniques
used to study adsorption-desorption characteristics of scale
346 Water-Formed Scale Deposits

inhibitors used in oilfield squeeze treatments (1971 and Spriggs and HooverIz1presented some detailed field studies
1973). of their experience with scale inhibitor squeeze programs in
Bradley1I9made the most recent detailed study on the in- west Texas (1972). Vetter'zz recently examined the means
hibition of calcium carbonate scale in water injection wells. by which barium sulfate scale deposits from water in deep,
Of particular interest in this study is the effect of pressure on high-pressure gas wells (1972).
inhibitor efficiency. Bradley used a special high-pressure
test apparatus in this study to simulate the pressure in an in- Chemical Scale Inhibitors in the Petroleum Industry
jection well (1972).
Ralstonl2O described the use of threshold treatments with Highly mineralized waters are associated with most oil
phosphonates, amine phosphates, polyphosphates, and and gas production. The total dissolved solids in these
polyacrylates to prevent water-formed deposits (1972). waters varies, but can be higher than 350,000 mg/l, such as
Table 8.8. The Need for a Variety of Chemical
Scale Inhibitors in the Petroleum Industry
0 Types of waters vary from a distilled water such as that in
boilers or gas condensate wells to natural brines or evaporated
seawater having 300,000 ppm dissolved solids plus suspended
solids.
0 Oils and distillates vary chemically as much as waters.
0 Solubility of chemicals varies in each one of the oils or waters.
0 Ratios of oil and waters vary.
0 Production techniques vary.
0 Temperatures and pressures vary.
0 Economics: cost of chemicals
cost of handling
Freezing: geographical variations - -freezing vs. evaporation

Table 8.9. Effect of Scale Inhibitors on Calcium Carbonate

(Static Precipitation Tests)
Effect of Temperature on Inhibitor Effectiveness (CaCO3 Precipitation)
(Cm: 2 X 10-3 mol; NaCl: 0.5 mol = 2.92%)
Percent of Potential PreciDitate KeDt in Solution
Inhibitor
Concentration
I Polyelectrolyte
I Ester
I Phosphonate
(PPm) 73°F 210°F 350°F 73°F 210°F 73'F 2lO'F 350°F
0 0 0 0 0 0 ~ 0 0 0
2 41 0 0 40 I 100 10 I
4 100 0 0 100 10 1 0 100 20 10
8 100 20 0 100 15 ~0 100 50 35
12 100 32 10 100 25 0 100 100 38
20 100 35 20 100 55 0 100 100 42
50 100 40 40 100 65 0 100 100 42
250 100 100 50 100 65 0 100 100 45

Inhibitor Polyelectrolyte Ester Phosphonate

Concentration
(PPm)
0
2
4
8
I 41:
100
100
0
0
Cm=2xlO-3 M
0
40
100
100
Cm=lO-I M
0
0
0
1
C1n=2xlO-~M
0
100
100
100
Cm = 10-1 M
0
0
0
0
12 100 2 100 2 100 1
20 100 10 100 10 100 2
50 100 12 100 30 100 15
100 45 100 50
After Vetter, 1970.2
 Test Methods and Chemical Inhibition Practices 347

those from the Smackover in Mississippi. The dissolved
solids are predominantly sodium chloride but may contain
large amounts of many other salts. In some cases the water
represents only a fractional percent of the total produced
fluids; in other cases the production may contain as high as
98% water.
During production these waters undergo changes that
tend to unstabilize and precipitate the mineral matter. The
simple precipitation of mineral components can be tolerated
under some conditions. However, the adherence of hard
masses results in mineral scale deposits that interfere with
production operations.
Scale deposits normally hamper fluid flow, prevent effec-
tive heat transfer, have an effect on corrosion processes, etc.
These deposits usually result in delays and shut downs for
removal, and they can be a safety hazard. Scale is an expen-
sive problem in almost any system handling water.
Precipitating or exchanging ions has seldom been of prac-
tical benefit in hydrocarbon producing operations because
volumes of water are usually large, solid concentrations are
extremely high, and produced waters cannot be segregated,
stabilized, or treated by such methods downhole (before be-
ing brought to the surface).
Numerous methods of dealing with mineral scale deposi-
tion in the oil and gas industry have been tried. These
methods have involved various typical water treatments
such as:
1. Pretreating water to remove scale-forming con-
stituents
2. Treating to prevent or delay deposition
3. Removal of previously deposited scale by chemical,
mechanical, or a combination of these methods.
Over the past few decades chemicals have been used ex-
tensively in scale prevention. Some of the devices mentioned
previously have also been used, in limited cases, for the
prevention and removal of scale, but the lack of success with
these devices in oilfield waters has limited their use.
Chemical inhibitors, however, have been successful in the
petroleum industry and there are a large number of products
used simply because of the wide variation in environments.
Some of the factors contributing to the need for a variety of
scale inhibitors are listed in Table 8.8.
Vetter made an interesting comparison of some of the
new commercially available phosphonate, polyelectrolyte,
and phosphate ester scale inhibitors on the precipitation of
calcium carbonate, calcium sulfate, and barium sulfate at
two concentrations and three temperatures. The results of
these static precipitation tests are shown in Tables 8.9, 8.10,

Table 8.10. Effect of Scale Inhibitors on Calcium Sulfate Precipitation

(Static Precipitation Tests)
Effect of CaS04 Supersaturation on Inhibitor Effectiveness
(Temperature: 210°F; NaCl: 0.5 M = 2.92%)
Percent of Potential Precipitate Kept in Solution
Inhibitor I Pol yelectrol yte I Ester 1 Phosphonate
Concentration I
(PPm) C m = 4 . 5 ~ 1 0 -M
~ C m = 8 ~ 1 0 -M
~ Cm=4.5x10-2 M Cm =8x 10-2 M Cm=4.5x10-2 M Cm = 8x10-2 M
0 0 0 0 0 0 0
2 0 0 85 0 70 0
4 50 0 90 2 80 2
8 70 0 90 4 85 4
12 80 0 95 10 90 6
20 90 0 100 10 100 8
50 100 0 100 20 100 15
250 100 0 100 30 I
100 80

Inhibitor Pol yelectrolyte Ester Phosphonate

Concentration
(PPm) 73°F 210°F 350°F 73°F 210°F 350°F 73°F 210°F 350°F
0 0 0 0 0 0 0 0 0 0
2 0 0 0 2 0 0 2 0 0
4 15 0 0 60 2 0 4 2 0
8 70 0 0 80 4 0 20 4 2
12 80 0 0 90 10 0 40 6 8
20 80 0 0 90 10 0 40 8 10
50 80 0 0 90 20 0 70 15 20
250 90 0 0 90 30 0 90 80 20
348 Water-Formed Scale Deposits

and 8.11. These data showed that the polyelectrolyte is
effective in decreasing order BaSO,>CaCO3>CaSO4. It
was particularly effective on BaSO,. The phosphate ester
had an effectiveness order of CaSO,>BaSO,>CaCO, but
was ineffective at high temperatures. The phosphonates
were the best inhibitors for CaC03 and also showed good
effectiveness in the high-temperature inhibition of BaS0,
and CaS04. These differences in the effectiveness of some of
the best commercially available inhibitors further illustrate
the need for a variety of scale inhibitors.
The simple fact that a chemical will prevent or delay scale
deposition is not enough to justify its consideration as a
scale inhibitor. Serious secondary problems are often
created by the use of a scale inhibitor, particularly in
petroleum operations. These problems can be more severe
or costly than the primary scale problem.
Those concerned with the study, development, use or
market of chemical scale inhibitors are not always aware of
the many secondary properties that should be considered in
addition to whether the product works as a scale inhibitor.
Some comments in regards to both primary and secondary
properties of scale inhibitors used in the petroleum industry
should be of benefit to those concerned with such problems.
What Type of Scale Occurs?
The three main types of mineral scale deposits en-
countered in the oil and gas industry are calcium carbonate,
calcium sulfate, and barium sulfate. They are rarely found
in their pure form; and more often than not, they are found
in combination with one another. These deposits can also
contain silica, strontium sulfate, iron compounds, bacterial
slimes, hydrocarbons, etc.
Typical examples of these problems appear throughout
this book. In order to combat the scale deposition problem
in the oil and gas industry, a concerted effort has been
directed toward the development of chemical inhibitors
specific to these types of scale.
What Types of Chemicals Are Used?
Many types of chemicals and chemical combinations
have been tried as scale inhibitors. Numerous products have
been patented, but only a few have actually become widely
used. Inorganic polyphosphates have been very successful in
controlling scale deposition in oil and gas operations. The
inorganic polyphosphates are highly efficient and economi-

Table 8.11. Effect of Scale Inhibitors on Barium Sulfate Precipitation

(Static Precipitation Tests)
Effect of Temperature on Inhibitor Effectiveness (Bas04 Precipitation)
(Cm: 5 X M; NaCl: 0.5 M = 2.92%)
Percent of Potential Precipitate Kept in Solution
~ ~~~ ~~~~~~~~~~~~ ~ ~

Inhibitor Pol yelectrolyte Ester Phosphonate

Concentration
(PPm) 73°F 210°F 350°F 73°F 210°F 350°F 73°F 210°F 350°F
0 0 0 0 0 0 0 0 0 0
2 100 80 0 100 100 0 100 100 0
4 100 90 20 100 100 0 100 100 5
8 100 100 40 100 100 0 100 100 9
12 100 100 60 100 100 0 100 100 30
20 100 100 100 100 100 0 100 100 55
50 100 100 100 100 100 0 100 100 100
250 100 100 100 100 100 0 100 100 100

Inhibitor Polyelectrolyte Ester Phosphonate

Concentration
~~ ~~~

(PPm) Cm =5x 10-4 M Cm=lxlO-3 M Cm=5xl0-4 M Cm=lxlO-) M Cm =5x M Cm= 1 ~ 1 0 M

-~
0 0 0 0 0 0 0
L 100 6 100 60 100 5
4 100 40 100 100 100 60
8 100 70 100 100 100 100
12 100 90 100 100 100 100
20 100 100 100 100 100 100
50 100 100 100 100 100 100
250 100 1
100 100 100 100 100
After Vetter. IS 2

Test Methods and Chemical Inhibition Practices
cal. Scale inhibitors containing inorganic polyphosphates do
have some limitations related to hydrolytic and thermal
stabilities as well as compatibility problems in high hardness
brines, and other materials must be used to overcome these
limitations.
Scale inhibitors based on partially hydrolyzed low
molecular weight polyacrylamides or low molecular weight
polyacrylate derivatives have been widely used during the
past several years. Organic phosphates, organic
phosphonates, and derivatives of these materials such as low
molecular weight esters have been used extensively for scale
inhibitors because they exhibit many of the desirable sec-
ondary properties needed in scale inhibitors. The basic scale
inhibitor chemical is usually formulated with other
materials as a liquid in order to meet the many demands of
field handling operations.
How Do Scale Inhibitors Work?
Scale inhibitors used in the oil industry function by many
of the mechanisms previously discussed. Under certain con-
ditions various chemicals can be used to delay, reduce, or
even eliminate scale deposition. Many mechanisms have
been proposed for the way or ways chemical scale inhibitors
function. Briefly, some of these mechanisms involve the
ability of the chemicals to function as
1. Dispersants
2. Anti-precipitants
3. Sequesterants
4. Chelating agents
5. Crystal modifiers
6. Sludge conditioners, etc.
With the exception of the sequesterants, such as
ethylenediamine tetraacetic acid (EDTA) and nitrilotria-
cetic acid (NTA), most of the scale inhibitors are thought to
alter crystal morphology. Some of the more widely used
scale inhibitors, such as the inorganic and organic
phosphorus derivatives, are known to function by several
mechanisms. For example, phosphorus-containing
derivatives used at high concentrations, in some instances,
can sequester potential scale-forming cations. At lower con-
centrations these same materials will allow precipitation but
will prevent adherence by functioning as a dispersant and by
altering the size of the crystal and/or preventing growth of
nuclei.
Alteration in crystal morphology is one of the main
mechanisms by which most scale inhibitors used in oilfield
environments are thought to function. How this alteration
in crystal size and shape results in less adherence is not well-
understood at this time.
How Are Scale Inhibitors Used?
Scale inhibitor applications are much more diverse in
producing wells than they are in disposal or injection wells.
This is mainly due to the wide variations in completion
techniques and downhole equipment. For example, the
method of applying liquid scale inhibitors will vary depend-
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349
ing on whether a well is produced by natural pressure from a
gas or water drive, whether it is pumped with a rod pump,
submersible electric pump, a hydraulic power oil pump, or is
produced by gas lift.
Sometimes inhibitors are added to water or alcohol and
are injected with the gas in a gas lift operation. Gas is in-
jected down the annulus through special valves and this
blows the fluid above the gas out of the tubing. It is then
separated from the liquids on the surface and is reinjected.
Scale inhibitors added to the gas will sometimes dehydrate
and plug the gas lift valves, particularly where the gas has
increased in temperature due to the compression required to
raise its pressure for reinjection. Substantial water dilution
will usually solve this type of problem.
Liquid scale inhibitors are often added to the power water
or power oil in wells pumped by submersible hydraulic
pumps. Compatibility problems with other chemicals often
occur since corrosion inhibitors, biocides, paraffin in-
hibitors, and demulsifiers are commonly needed in these
fluids.
Some scale inhibitors are applied in solid forms, such as
powders, briquettes, or balls. These are used in perforated
baskets, by-pass feeders, fracturing operations, or are
dumped downhole. Most of the chemicals, however, are
handled as liquids, and most of the liquids are water-based
formulations. Liquid products are desirable for several
reasons in producing operations. Liquid chemical feeders .
are usually more accurate and more dependable than dry
chemical feeders, and the use of a liquid also eliminates the
step of dissolving the scale inhibitor in the produced fluids.
Liquid scale inhibitors are used most successfully and most
often on continuous bases, usually at concentrations of 1 to
20 ppm. They are injected into the producing fluids by gas,
electric, or beam-operated chemical pumps.
Liquid scale inhibitors used in the oil industry must be
formulated to deal with all of the problems mentioned under
“Formulated Products.” These include minimum freezing
and pour points, minimum corrosion characteristics, high or
no flash points, minimum toxicity, no separation problems,
minimum evaporation problems, minimum bacterial
degradation, etc.
A more recent treating application, performed by squeez-
ing a scale inhibitor back into a formation, allows the
chemical to be placed with low-pressure portable pump
units without fracturing the formation, which occurs when
solid scale inhibitors are used. The chemical is adsorbed
and/or partially precipitated in the formation and is slowly
released with the produced fluid to provide long-term con-
tinuous scale inhibition. Fifteen to 200 gallons of scale in-
hibitor, depending on well conditions, can provide 3 to 24
months scale inhibition. The scale inhibitor squeeze treat-
ment is becoming one of the major methods of applying
scale inhibitors. This application requires the scale inhibitor
to have certain secondary properties. Some of the details of
these various uses will be examined.
Continuous Treatments
The effective use of scale inhibitors almost demands their
use on a continuous basis. Unlike film-forming corrosion in-