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Summary During acidizing, acid must reach the formation at its original
Pickling well tubulars to prevent pumping unwanted materials into the strength and contain as few contaminants as possible for the job
formation is an issue that should be decided on an individual-job basis. to have maximum effectiveness. Pickling the tubing before acid
Acid pickling of tubing is a process of flow in a tube or an annulus jobs removes scale and other contaminants and allows successful
with heterogeneous reactions occurring at the wall of the tube. The treatment. In hydraulic fracturing, the scouring action of the prop-
reacting solid species at the wall are primarily mill scale and other pants on the tubing mixes mill scale, pipe dope, and other tubular
types of inorganic scale. The fluids injected for pickling are usually contaminants into the main fracturing fluids during proppant
strong acid solutions [hydrochloric acid (HCl)] but also may include transportation. These materials can be introduced into the forma-
surfactants, organic solvents, and gelled solutions to aid in lifting sol- tion and may reduce the conductivity of the fracture. In addition,
ids from the wellbore. Thus, the process is a complex one involving these materials are capable of damaging the formation or plugging
several reactions and perhaps multiple stages of fluids. the perforations and, therefore, must be removed from the tubing
Tubing pickling is an essential part of well-stimulation treat- before pumping the main treatment fluids.
ments if the main acid is to be bullheaded. Standard design param-
eters for a pickle treatment depend on experience and personal
Description of the Process
judgment. It appears that the standard pickle-treatment design is
overestimating the required volume of pickling acid. Field data In a tubing-pickling treatment, several tubular contaminants are
indicated that excessive acid volumes were used for tubing pickling reacting with the acid as it flows through the pipe. Reactions of
because large returns of unreacted (live) acid were recovered at these contaminants with the acid are classified as heterogeneous
the surface. Careful analysis of flowback samples obtained from reactions because they are liquid/solid reaction systems. Fig. 1
several deep gas wells showed that only a fraction of the acid was depicts the way the acid enters, reacts with, and exits the pipe. Part
consumed by mill scale and other tubing contaminants. A shows the system before the acid enters the pipe. Once the acid
In this paper, proposed mechanisms are presented to explain enters the pipe, as indicated in Part B, it starts reacting with the
the behavior of acid contact with the tubing and a mathematical inner surface of mill scale, forming a slug of spent acid (reaction
model is developed to predict acid consumption and dissolution of products) in front of the live acid. As the acid travels farther down
tubular contaminants. The model applies to the bullheading case the pipe, as in Part C, it is consumed by the mill scale, creating a
where the acid is pumped down the tubing and then flowed back larger spent-acid slug. Part D shows the displacement fluid push-
to the surface. The model considers the reaction of acid with mill ing the acid forward in the pipe. The volume of the live-acid slug
scale (Fe3O4). The equations formulated are solved numerically to decreases, while that of the spent-acid slug increases as the acid
predict the concentrations of major chemical species in the well travels farther down the tubing. That is because the front of live
flowback samples. acid is converted to spent acid by the reaction.
Such a model is extremely valuable in optimizing future pick- A careful review of actual field data supports the idea of this
ling treatments. The acid volume needed for pickling operations mechanism. Fig. 2 shows the total iron concentration (main reac-
can be reduced significantly, and other improvements can be made tion product) in the acid front, mainly in the region occupied by the
without extensive and costly field testing. Finally, recommenda- spent acid (Nasr-El-Din et al. 2002b). Because the chloride ion is
tions are given to design acid-pickling treatments better. not consumed in the reaction, it can be used as a tracer. Therefore,
we can identify the region between the live-acid and the chloride-
Introduction ion curves as the spent-acid slug (Fig. 3).
Figs. 2 and 3 suggest that only the front of the live acid is
The main purpose of the chemical stimulation treatment is to remove
reacting with mill scale. Hence, if the whole slug of live acid is
formation damage and enhance well productivity. The treatment nor-
reacting, then high levels of iron would appear over the whole
mally consists of acids, solvents, surfactants, gels, or combinations
interval. It is important to note that the amount of mill scale in a
of these chemicals. When these treating fluids are pumped through
well is limited. Only a very thin layer of scale (0.01 in. thick) is
the injection or production tubing, they may squeeze contaminants
available for the reaction (Smith 1990). As described, mill scale is
from the tubing into the formation, which may plug the perforations
removed during the reaction with the early flow of acid. The fresh
or damage the formation (McLeod 1984). Therefore, the purpose of
acid that comes later is in excess and does not find scale to react
the tubing-pickling treatment is to clean the injection or production
with until the acid advances to unreacted scale down the tubing.
tubing of damaging material before conducting the main stimula-
The fresh acid is inhibited with corrosion inhibitors, which prevent,
tion treatment.
or at least reduce, the dissolution of well tubulars.
In general, a tubing-pickling treatment is a prerequisite if treat-
The preceding has described the macroscopic picture of the
ing fluids, such as the acid in acidizing treatments, or the fluid
problem by considering the whole system. In Fig. 4, a microscopic
transporting sand particles, as in gravel packing, are to contact
visualization demonstrates the proposed mechanism of the hetero-
both the tubing and the formation during the main treatment. The
geneous reaction between the acid and the reactants on the inner
main purpose of tubing pickling is to remove mill scale, rust, iron
surface of mill scale. Two main processes control the reaction (Wil-
sulfide, and pipe dope from the tubing.
liams et al. 1979; Loewen et al. 1990; Nasr-El-Din et al. 2002b):
• Mass transfer—This process includes the transfer of the react-
ing species from the bulk of the acid to the surface of the mill scale
Copyright © 2010 Society of Petroleum Engineers
and then the transfer of the reaction products from the surface of
This paper (SPE 93291) was accepted for presentation at the SPE International Symposium the scale back into the bulk stream.
on Oilfield Chemistry, The Woodlands, Texas, USA, 2–4 February 2005, and revised for
publication. Original manuscript received for review 15 May 2008. Revised manuscript
• Reaction kinetics—The rate of the reaction between the acid
received for review 18 November 2009. Paper peer approved 21 October 2009. and mill scale that coats the inner surface of the tubing.
120000 24
60000 12
20000 4
0 0
0 50 100 150
D. The original fluid exited the pipe. Displacing fluid pushing
Flowback Time, min
the acid.
Fig. 2—Fe and HCl concentrations in well flowback samples
for Well A.
1.2 125000
HCl
1 Chloride
100000
Dimensionless HCl and Cl –
Fe
Iron Concentration, mg/L
0.8
75000
0.6
50000
0.4
25000
0.2
0 0
0 20 40 60 80 100 120 140
Flowback Time, min
MILLSCALE LAYER
Outer Radius of the Tubing
Transport to the scale surface
scale is uniform throughout the tubing. However, Smith (1990) tives on the reaction rate were not considered when developing the
claimed that the soft layer (0.007 in.) may pop off the pipe during model. However, the presence of the corrosion inhibitor was used
straightening and handling. Once a new pipe is placed in a well, to support the idea of minimal attack on the base metal by the acid.
higher temperatures will enhance the corrosion rate and the scale Water-wetting surfactants removed any residual hydrocarbons and
film becomes thicker. The nonuniform temperature along the enhanced acid/mill-scale contact.
tubulars makes the growth rate of the scale layer nonuniform as In order to visualize the problem, consider a cross section of the
well. Therefore, it is expected that the thickness of mill scale will pipe as shown in Fig. 5. Before the acid contacts the scale, it has an
increase with depth. original radius a0. The radius then increases to a new larger value
a as the acid stays in contact with the scale for a time increment
Development of a Mathematical Model t. The volume of magnetite dissolved during this time interval is
When the acid enters the pipe, it reacts with a thin layer of magne- given by (Al-Mutairi 2004)
tite deposited on the inner surface of the scale. Therefore, the inside
diameter of the scale layer becomes relatively larger as the acid ∂a kCHCl MWHCl
= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
dissolves more magnetite. The amount of dissolved magnetite and, ∂t Fe3O4
hence, the effect on the inner diameter of the scale layer increases
as the acid contact time with the pipe increases. Thus, there exists Using appropriate dimensionless transformations, Eq. 3 is con-
a critical contact time at which all the magnetite will be consumed verted to
and extra exposure time will not be beneficial.
Several assumptions were made in developing the mathematical ∂
= DK HCl , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (4)
model. It was first assumed that the effect of the acid on the base ∂
metal of the pipe was minimal. This was because of the presence of
a sufficient amount of proper corrosion inhibitor in the live acid. On where , HCl, and are dimensionless groups for the radius, acid
the basis of this assumption, radius enlargement caused by subse- concentration, and time, respectively.
quent live-acid contact with the base metal was neglected. Further,
isothermal conditions were assumed during acid pumping and well kL
D= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (5)
flowback. In other words, the variation in temperature with depth a0u
was neglected. Also, temperature variations caused by the heat of
the reaction were neglected. Acid concentration was a function of and
the axial position and time only. There was no radial change in the
(C )
acid concentration. Therefore, the problem was described by axi- 0
HCl MWHCl
symmetric cylindrical flow. This assumption was well justified K= . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)
Fe3O4
because of the turbulent-flow conditions that were present during
the acid-pickling treatments. The mill scale was assumed to be
distributed evenly over the surface of the tubing. In other words, the Eq. 4 describes the change of the radius at each axial position
scale thickness was independent of the axial position in the pipe. in the pipe as the acid reacts with the scale. One known condition
Transport of reactants to the inner surface of the scale or reaction is that the radius of the scale, at a certain point, will not change
products by diffusion was accounted for by numerical dispersion. until the acid reaches this point. Thus,
Mixing that might be induced by produced gases during flow-
back was not considered in the model. This mixing was noted for ε > , ( , ε ) = 1 , . . . . . . . . . . . . . . . . . . . . . . . . . . (7)
in the flowback analysis of a few wells, and its effect on model
predictions was not significant. Finally, the effects of acid addi- where ε represents a dimensionless length.
∂CCl − ∂CCl −
∂CHCl ∂C 2 kCHCl = −u . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (18)
= − u HCl − . . . . . . . . . . . . . . . . . . . . . . . . . . (8) ∂t ∂x
∂t ∂x a
Using appropriate dimensionless transformations, Eq. 18 is
Using appropriate dimensionless transformations, Eq. 8 is trans- transformed to
formed to
∂ Cl − ∂ Cl −
∂ HCl ∂ HCl + = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (19)
+ + DM HCl = 0 , . . . . . . . . . . . . . . . . . . . . . . . (9) ∂ ∂ε
∂ ∂ε
The following initial and boundary conditions accompany Eq.
where 19:
Cl ( 0, ε ) = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (20)
(
⎡ C0 ⎤ )
M = ⎢ 2 0 ⎥ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (10)
HCl
⎢ CHCl ⎥
⎣ ⎦
⎧1, during pumping the acid
Cl ( , 0 ) = ⎨ . . . . . . . . . . . . . . . (21)
The first term in Eq. 9 represents the accumulation of the acid at ⎩ 0, otherwise
any point in the tubing. The second term describes the transport
of the acid through the tubing. And the third term represents the Eq. 19 is a linear, first-order partial-differential equation. It
depletion of the acid by the reaction with mill scale. describes the propagation of chloride ion in the wellbore during
Because there is no acid present initially in the tubing, we pickling treatment. Eqs. 9 and 14 are nonlinear first-order partial-
have differential equations. This system of equations was solved using
numerical techniques. Space derivatives were approximated using
HCl ( 0, ε ) = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (11) central finite differencing, whereas backward finite differencing was
used to approximate time derivatives. This approximation method is
called upwind differencing. The accuracy of this method depends on
Also, the concentration of the acid at the tubing inlet is constant the values of and ε. It is known that the solution of the equations
during pumping the acid. Thus, using this method is stable as long as (/ε) < 1. It should be noted
that the values of and ε used in the present study were 0.0002
and 0.0005, respectively. This means that /ε was 0.4.
⎧1, during pumping the acid
HCl ( , 0 ) = ⎨ . . . . . . . . . . . . . . (12)
⎩ 0, otherwise Field Application
Tubing-pickling treatments of two wells (A and B) were used to
In a similar way, the mole balance on the total iron gives validate this model. The two wells were completed with 5½-in. 20#
NK-3SB C-95, low-carbon steel tubing. The tubing was 10,850 and
10,040 ft long for Wells A and B, respectively, and both wells had a
∂CFe ∂C ⎛ 3 ⎞ kC 4.778-in. inner diameter. Other pertinent data are given in Table 2.
+ u Fe − 2 ⎜ ⎟ HCl = 0 . . . . . . . . . . . . . . . . . . . . . (13)
∂t ∂x ⎝ 8⎠ a Acid additives included a corrosion inhibitor and a water-wetting
agent. More details on the acid formulation were given by Nasr-El-
Using appropriate dimensionless transformations, Eq. 13 is trans- Din et al. (2002b). It is important to note that the gases produced
formed to from these wells contained hydrogen sulfide. Therefore, a hydrogen
sulfide scavenger was added to the acid. More details on hydrogen
sulfide scavengers were given in Nasr-El-Din et al. (2002a).
∂ Fe ∂ Fe In both wells, pickling fluids were pumped down through the
+ − DG HCl = 0 , . . . . . . . . . . . . . . . . . . . . . . . . (14)
∂ ∂ε production tubing until the leading edge of the acid was 50 ft
above the upper set of perforations. Then, the acid was flowed back
where immediately through the same path to the surface using reservoir
pressure. A total of 4,000 gal of 20 wt% HCl was used to pickle the
tubing of Well A (a perforated gas well). The estimated flowback
( )
⎡6 C0 ⎤
G=⎢
HCl
⎥ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (15) rate for Well A was 1.7 bbl/min, while the acid pumping rate was
⎢ 8 CFe0 ⎥ 3 bbl/min. Flowback rate was based on the time required to flow
⎣ ⎦ back the 4,000 gal of acid. Well B was pickled with only 2,000 gal
of 20 wt% HCl. It was also a perforated gas well. The estimated
As with Eq. 9, Eq. 14 has the accumulation and transport terms.
flowback rate for Well B was 3.7 bbl/min, while the acid pumping
The last term in Eq. 14 represents the loading of iron, which bal-
rate was 3 bbl/min. Flowback rate was based on the time required
ances the depletion-of-the-acid part in Eq. 9. Eq. 15 represents
to flow back the 2,000 gal of acid.
the stoichiometry between the acid and the iron in the chemical
After pickling Well A, samples of well flowback were collected
reaction (Eq. 1). The set of initial and boundary conditions for the
once per minute for the first 37 minutes. Then the well was shut in
total iron can be given as
for 17 minutes because of operational problems, and no samples were
collected. Sampling was resumed once the well was put on production,
Fe ( 0, ε ) = 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (16) and sampling was conducted every 3 to 4 minutes. This relatively short
1.2
Squares: Actual Chloride Concentration
Solid Line: Modeled Chloride Concentration
Dimensionless Cl– Concentration, ψCl
0.8
0.6
0.4
0.2
0
0 0.5 1 1.5 2
Dimensionless Flowback Time, θ
Fig. 6—A comparison of actual and predicted dimensionless chloride concentration for Well A.
0.8
1500
0.6
1000
0.4
500
0.2
0 0
0 0.5 1 1.5 2
Dimensionless Flowback Time, θ
Fig. 7—Predicted dimensionless concentrations of iron and chloride for Well A.
show comparisons of model predictions with field data. It should slug. This resulted in more dispersion and tailing of the profile
be noted that, when bullheading the acid, the fluid that was pumped of the chloride ion. The high mixing and dispersion effects were
last would flow back first. This means that the acid front appeared escalated by the 17 minutes of shut-in time during well flowback.
toward the tail end of the acid slug. However, the effect of gases produced during well flowback on the
The dimensionless chloride concentration is shown in Fig. 6 as maximum iron and amount of iron dissolved by the acid was not
a function of dimensionless time. The dimensionless chloride con- significant, as will be shown in the following.
centration was almost zero in the initial stages of well flowback. The way the fluids are pumped in and out of the wellbore
Then, it reached unity at a dimensionless time of 1.2. Finally, the affected the time when various species were produced. Fig. 7
chloride concentration gradually decreased and exhibited some- shows the dimensionless concentrations of chloride (tracer) and
what of a tailing effect in the very last stage of well flowback. iron ions as a function of the dimensionless time. The iron peak
A good agreement between the model predictions and field data was expected to appear in the flowback samples toward the end of
was obtained at dimensionless time of 1.2. However, model predic- the acid slug. The chloride ion was noted first in the well flowback
tions were not as close to the field data for the very last stage of samples and was followed by iron.
flowback. This difference is mainly because of the flow of gases Fig. 8 shows the dimensionless acid concentration as predicted
during well flowback. The flow of gases through wellbore fluids by the model and obtained from field data. Reaction occurs at
during well flowback increased mixing and dispersion of the acid late times where the acid contacted the tubing first. Fig. 9 shows
1.2
Circles: Actual HCl Concentration
Dimensionless HCl Concentration, ψHCl
0.8
0.6
0.4
0.2
0
0 0.5 1 1.5 2
Dimensionless Flowback Time, θ
Fig. 8—Predicted and actual dimensionless acid concentration for Well A.
1500
1000
500
0
0 0.5 1 1.5 2
Dimensionless Flowback Time, θ
Fig. 9—Predicted and actual dimensionless iron concentration for Well A.
the actual and predicted dimensionless iron concentrations. The Finally, the model was used to optimize the acid-pickling treat-
actual and simulated maximum iron concentrations were 105 488 ments. Two main parameters were examined: the reaction-rate
and 107 203 mg/L, respectively. The actual and simulated total constant and the acid pumping rate. Parameters of Well A (Table
amounts of iron produced in the well flowback were 1027 and 2) were used in the optimization process.
1040 kg, respectively. The chloride ion was used to track the Fig. 10 and Table 4 show the maximum iron concentration and
emergence of acid from the tubing because field data were sampled total amount of iron removed as a function of the reaction-rate con-
randomly. Then, proper alignment was performed to match the stant. Reaction-rate constants greater than 1×10−5 m/s will ensure
field and model data. Simply, the actual time was converted to removing all of the mill scale from the tubing. On the other hand,
dimensionless time. lower reaction-rate constants do not provide good cleaning with the
The results shown in Figs. 6, 8, and 9 indicate that the model current amount of acid. Matching the field data with model predic-
predicted field data very well. The effect of mixing caused by the tions indicates that the best value for the reaction rate constant is
presence of gases produced during well flowback was found to be 6.95×10−6 m/s, which is in good agreement with the data given by
not significant in the wells examined. Cumper et al. (1982).
160000 1200
1000
Maximum Iron Concentration, mg/L
120000
800
Amount of Iron, kg
80000 600
400
40000
200
Maximum Iron
Concentration
0 0
1×10–7 1×10–6 1×10–5 1×10–4 1×10–3 1×10–2
Reaction-Rate Constant , m/s
Fig. 10—Effect of reaction-rate constant on the maximum iron concentration for Well A.
120000
60000
30000
0
0 2 4 6 8 10 12
Flowrate, bbl/min
Fig. 11—Effect of the acid pumping rate on maximum iron concentration for Well A.
The effect of the acid pumping rate on the iron peak is examined Well B. The thickness of the scale for Well B was estimated from
in Fig. 11 and Table 5. The data show that the iron peak decreases the treatment data by integrating the total-iron-concentration curve.
when the acid pumping rate is increased. This result is reasonable The total amount of iron removed from the tubing was found to
because slow rates would give more contact time and allow the be 140.5 kg. This amount of iron was divided evenly on the total
acid front to be loaded with more iron. It is clear that the iron peak inner surface area of the tubing to obtain a scale thickness of 0.001
increases with increasing the dimensionless parameter D (Eq. 5). in. The difference in the amount of the dissolved iron is because
This parameter increases with increasing the reaction-rate constant the tubing of Well A is longer and older.
or by decreasing the acid pumping rate. Table 3 lists values of dimensionless variables for the pickling
Fig. 12 shows the effect of the acid pumping rate on the amount treatment that was conducted on Well B. The values of D, K, and
of iron dissolved by the acid (the cleaning process). High pumping G were calculated to be 1.923, 0.035, and 2,520, respectively.
rates do not give ample contact time for all the scale to be removed. The shorter length of the tubing of Well B and the increase of the
However, for this example, flow rates as high as 4 bbl/min still pumping rate caused the parameter D for Well B to be different
give good results. from that of Well A. The values of K and G did not change because
In field application, the practical limitations for the acid pump- they reflected the properties of the fluids used and scale, which
ing rate (maximum = 5 bbl/min) can ensure sufficient contact time did not change. Figs. 13 through 15 show comparisons of model
for scale removal. This is indicated by the flat section of the iron predictions with field data for Well B.
curve shown in Fig. 12. This section means that the contact time The dimensionless chloride concentration is shown in Fig. 13
provided by 4 bbl/min was sufficient to remove all the scale and as a function of dimensionless time. A good agreement between
that more contact time provided by the lower flow rate was not the model predictions and field data was obtained at dimensionless
needed. If the volume of acid were increased, then the flat section
would cover even higher flow rates because the contact time would
increase. For example, with 8,000 gal of acid, the flat section in
Fig. 12 would cover up to 7 bbl/min. TABLE 5—EFFECT OF ACID PUMPING RATE
ON IRON REMOVAL, WELL A
1000
Iron Removed, , kg
800
600
400
200
0
0 2 4 6 8 10 12
Flowrate, bbl/min
Fig. 12—Effect of the acid pumping rate on the amount of iron removed for Well A.
time of 1.05. Well B was not shut in during the flowback, as was acid from the tubing because field data were sampled randomly.
the case with Well A; therefore, the mixing and dispersion effects Then, proper alignment was performed to match the field and
of the acid slug were not noticed. As a result, a tailing profile of the model data. Simply, the actual time was converted to dimension-
chloride ion did not appear. The shock-like profile at both ends of less time.
the curve indicate that the viscous pills that were used to separate The results shown in Figs. 13 through 15 indicate that the model
the acid slug from other stages were effective. predicted field data very well. The way the fluids are pumped in
Fig. 14 shows the dimensionless acid concentration as predicted and out of the wellbore affected the time when various species were
by the model and obtained from field data. Reaction occurs at late produced. Fig. 16 shows the dimensionless concentrations of the
times where the acid contacted the tubing first. Fig. 15 shows the HCl, the chloride, and the iron as a function of the dimensionless
actual and predicted dimensionless iron concentrations. The actual time. As was discussed earlier and shown in Figs. 2 and 3, the
and simulated maximum iron concentrations were 90 436 and iron peak appeared in the flowback samples toward the end of the
90 699 mg/L, respectively. The actual and simulated total amounts acid slug. The loss of the acid was substituted by a gain in iron
of iron produced in the well flowback were 145.5 and 140.6 kg, concentration. The model gave good explanation of the pickling
respectively. The chloride ion was used to track the emergence of process, which agreed with our interpretation in Fig. 2.
1.2
1
Solid Line: Modeled Chloride Concentration
0.8
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Fig. 13—A comparison of actual and predicted dimensionless chloride concentration for Well B.
HCl
1 Solid Line: Modeled HCl Concentration
0.6
0.4
0.2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Dimensionless Flowback Time, θ
Comparison between the model and the actual results measured time for reaction to dissolve the scale from tubing totally. However,
in the field is summarized in Table 6. It is shown that the model some extra acid is recommended as an allowance. The allowance
predicted the final outcome of the pickling treatments accurately. should provide enough acid to exit with the same acid strength.
The difference between model prediction and actual field data The following formula is recommended to calculate the volume
varied from one case to another, with a maximum of 10%. It is of 20 wt% HCl acid (V in gallons) required to remove magnetite
believed that the main source of this difference is the simplifying from the tubing or the liner:
assumptions made in the development of the model.
V = 4.6874 × ts × L × F(d + ts), . . . . . . . . . . . . . . . . . . . . . (22)
Procedure To Estimate Acid Volume
On the basis of the results obtained in the present study, the fol- where d = diameter of tubing or liner in inches, F = safety fac-
lowing procedure is recommended to determine the acid volume tor, L = length of tubing or liner in feet, and ts = thickness of the
required to remove the scale. scale in inches.
The required volume of acid should be calculated from the There is a maximum acid pumping rate that should not be
reaction stoichiometry between scale and the acid. This applies exceeded. This rate should give enough contact time for efficient
to current average pumping flow rates, which give ample contact cleaning of the tubing. This rate depends on the volume of the acid
2000
Dimensionless Iron Concentration, ψFe
1200
800
400
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
1600
Modeled Iron Concentration
1200
0.6
800
0.4
400
0.2
0 0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Fig. 16—Predicted dimensionless concentrations of chloride, HCl, and iron for Well B.
used. Exceeding the maximum rate will give insufficient contact • The pickling process was found to be affected by acid pump-
time and some of the scale will not be removed. For Well A, as ing flow rate and the reaction-rate constant (i.e., by Damköhler
noted in Fig. 12, flow rates as high as 4 bbl/min are permissible number).
without affecting the results. • A slight deviation between model predictions and field results
Finally, the best way to use this model is first to calculate the was noted in Well A because of mixing produced gases with spent
theoretical amount of acid needed to remove all the scale using acid. However, the effect of this on the amount of iron produced
Eq. 22. Second, identify the maximum flow rate that is planned and on the maximum iron concentration noted in the flowback
for the treatment. Then, use this flow rate with an amount of acid samples was not significant.
that is greater than the one calculated until the dimensionless acid
concentration in the flowback samples reaches unity. The amount Nomenclature
of scale removed from the tubing is independent of flow rates less a = inner radius of scale, m
than the one entered into the model. Therefore, unplanned lower a0 = initial inner radius of scale, m
flow rates will not affect the pickling process. CCl − = chloride-ion concentration, mol/m3
CCl0 − = initial chloride-ion concentration, mol/m3
Conclusions
CFe = total iron concentration, mol/m3
In this work, a mathematical model was developed to predict the CFe0 = initial total iron concentration, mol/m3
acid and total iron concentrations following acid-pickling treat-
CHCl = HCl concentration, mol/m3
ments when the acid is bullheaded. The following conclusions can
be drawn from this work:
0
CHCl = initial HCl concentration, mol/m3
• Acid-pickling treatment removed significant amounts of iron. There- d = diameter of tubing or liner, in.
fore, it is strongly recommended to pickle well tubulars before acid D = Damköhler number
treatments, especially when the acids will be bullheaded. k = reaction-rate constant, m/s
• Model predictions were in a good agreement with field results. K = acid capacity number