SPE 54721

Chelating Agents in Sour Well Acidizing: Methodology or Mythology

Michael M. Brezinski, Halliburton Energy Services

Copyright 1999, Society of Petroleum Engineers, Inc.

This paper was prepared for presentation at the 1999 SPE European Formation Damage
Conference to held in The Hague, The Netherlands, 31 May01 June 1999.
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Abstract
Metal chelating materials have been used as iron control
agents in acidizing treatments for many years. There are
several disadvantages associated with use of the various
commercially available products. These disadvantages include
low solubility and high toxicity. Furthermore, recent evidence
casts considerable doubt on the effectiveness of common
chelating agents for iron control in sour environments.
A relatively simple procedure will be presented that allows
preparation of pure metal (calcium and iron) chelant
complexes. These complexes serve as models for the in-depth
evaluation of various chelating agents over a broad range of
temperatures and fluid compositions and have been
characterized with respect to solubility and thermal stability in
spent acid fluids. The experimental results show loss of
solubility of calcium complexes as well as thermal
decomposition of ferrous complexes at relatively low
temperatures. Implications of these results will be discussed.
The problems are exacerbated in sour environments where
iron sulfide precipitation occurs at a very low pH. New
evidence will be presented that shows iron sulfide
precipitation will occur below the pH range where chelating
agents are effective. The precipitation of iron sulfide has been
found to be dependant upon formation basicity and NOT the
overall acidity of the bulk fluid as commonly believed. The
result implies that simple equilibrium calculations may not
reliably predict the chemistry that will occur downholeand
must be used with caution.
The conclusion drawn from these results is that the only
effective method of preventing precipitation of iron sulfide
during sour well acid treatments is to remove H2S from the
fluid with sulfide scavenger products. The elimination of large

quantities (6-36 kg/m3, or 50-300lbs./Mgal) of chelating

agents will have significant cost savings with regards to fluid
cost. The evidence provided in this paper shows that these
products are not effective and even worse, may precipitate in
the formation and cause severe damage
Introduction
Chelating agents (or sequestering agents) are commonly used
in well stimulation treatments1,2. The primary function of these
materials is to tie up or chemically bind hydrated metal ions
thus changing the ions reactivity. Effective chelation can
prevent unwanted and potentially damaging effects caused by
metal ions by reacting with components in the fluids (live or
return). For example, crosslinking and breaker properties can
be changed, thus causing rheological perturbations in fluid
characteristics and clean-up properties.
Probably the most common use of chelating agents is to
prevent precipitation of metal compounds in high pH fluids.
Iron(III) or ferric ion, readily undergoes hydrolysis in aqueous
solutions when the fluid pH becomes >2.5. This hydrolysis
reaction will produce iron(III) hydroxide, which precipitates
during HCl spending during an acid stimulation treatment.
Inclusion of chelating agents in the stimulation fluid is quite
effective in preventing the hydrolysis reaction and hence the
precipitation of the metal species.
Thus, chelating agents appear to be both beneficial to
stimulation fluids and chemically straightforward in function.
However, this is not necessarily true under all conditions. One
particular environment of concern, and the topic of this
manuscript, is that of systems containing hydrogen sulfide
(H2S). These systems contain only Fe(II) species. Fe(III), a
strong oxidant, is chemically incompatible with H2S, a strong
reducing agent. These two species react, forming Fe(II) and
elemental sulfur.
Answers to the following questions were sought:
1. At what point does FeS begin to precipitate from spent acid
fluids? Past experimental work is flawed and several different
values can be calculated from literature data.
2. What is the theoretical prediction of chelate complex
stability at pH values encountered in well stimulation

M. BREZINSKI

treatments? The usual formation constants are for neutral

conditions (pH7) and are far higher than return fluids will
reach.
3. What are the properties of both calcium and Fe(II) chelate
complexes? In particular, will calcium and iron complexes
remain in solution or precipitate (e.g. citrates have low
solubility)? If formed, do the complexes possess enough
thermal stability to survive downhole conditions? If the
complexes are not thermally stable, it will be likely that the
metal ions will be released negating the effect of the additives.
The answer to these questions requires preparation of the
complexes.
4. Can the Fe(II) complexes actually protect the metal center
from hydrogen sulfide and thus prevent formation of FeS in
the acidity range found for return stimulation fluids?
Obviously, if the complexes react with hydrogen sulfide, the
use of chelating agents will be of no value.
FeS Deposition Pathway
FeS precipitation from stimulation fluids has been
documented3,4. The accepted value marking the onset of this
potentially damaging reaction is pH=1.9. However, there are
several values available for the KSP of FeS as well as the Kas
of H2S. Crowe predicts the precipitation to occur at pH=1.9
from a solution containing 1000 PPM of both H2S and Fe (II)
ions3. The published demonstration of the validity of the
calculation is flawed in that the concentration of Fe(II) was
unknown (from the dissolution of a small quantity of steel
wool). Also, the solution was spent with calcium carbonate
chips to a final pH of 5 before the addition of H2S which
caused FeS to form. Dill, et. al. used Fe(III) in hydrogen
sulfide systems and therefore probably had little H2S
remaining (after oxidation to elemental sulfur by Fe(III))to
form FeS in their experiments4.
The KSP and equilibrium constants, which were obtained
from other sources, predict that much higher pH values may
be tolerated before the onset of FeS precipitation. For
example, pH = 3.2 and 3.75 are calculated from data taken
from the Handbook of Analytical Chemistry5 and Advanced
Inorganic Chemistry6 respectively. The following experiments
were designed to probe this apparent discrepancy.
These experiments were carried out anaerobically to avoid
oxidation of both Fe (II) and H2S. 20% calcium chloride water
was used to simulate spent 15% HCl. This fluid was
rigorously degassed using freeze-pump-thaw cycles on a
vacuum line. The iron concentration was 5,000 PPM, the pH
of the fluid was adjusted with dilute HCl, and H2S was
introduced using a gas dispersion frit. Table 2 shows the
results of the tests. There was no evidence of FeS formation at
pH values from 0 to 3. Only when the acidity had decreased to
a value of 4-5, did the fluid darken and form black solids.
Because these experiments gave values higher than the
accepted range, another experiment was carried out that
included the only possible missing reactant the formation.

SPE 54721

Table 3 shows the results obtained from this experiment.

Fluids at pH values of 0 and 1 evolved CO2 as acid spending
on the carbonate was substantial. The sample with a pH value
of two provided the key. The marble chip slowly turned black
after immersion into the reaction fluid. SEM analysis showed
the surface of the chip to be covered with microcrystalline
FeS. The bulk fluid remained clear and colorless. This result
implies a surface-assisted deprotonation of H2S followed by
precipitation of FeS. Formation basicity appears to be the
important driver of the precipitation reaction at these low pH
values. One could have clear, clean return fluids but still have
deposited large quantities of FeS in the formation. Carbonate
is a very basic anion. A saturated aqueous solution of sodium
carbonate possesses a pH of 12! This phenomenon may be
important in other areas as well (e.g., fracturing fluid matrix
contact). Thus, normal solution equilibrium calculations
should be used with caution in predicting downhole chemistry.
Theoretical Chelate Complex Stability
The following calculations show that it is not obvious
complexes of EDTA and NTA will possess adequate stability
to exist in the presence of hydrogen sulfide.
The relative stabilities of chelated metal ions can easily be
compared using the appropriate formation constant: log Kf.
For example, the log Kf values for Fe(III) with NTA and
EDTA are log 15.9 and log 25.1 respectively. The values for
Fe(II) and these common materials are much lower being log
8.8 and log 14.3 respectively. Still, these log Kf values are
high enough to give one the feeling that the metal ions will be
complexed and rendered 'inactive' with respect to currently
accepted damage mechanisms. However, it must be
remembered that these log Kf 's are calculated for the fully
deprotonated chelating agent; EDTA only achieves 98%
deprotonation when a pH of 12 is reached. Most of the species
in solution still contain unionized protons. This means that
even if there is a strong interaction of the chelant with a metal
ion, there will still be uncomplexed coordination sites
available for the very reactions we are trying to stop. Figure 1
shows a plot of the fractional composition of EDTA vs pH.
The curves clearly show that in the pH range of return fluids,
the chelating agent is mostly in the completely unionized,
mono-ionized, and di-ionized form. These species will not
protect all the coordination sites of the metal center neccessary
to prevent attack by hydrogen sulfide.
More realistic information with regard to the stability of
the complex at lower pH values must be obtained from
conditional formation constants, Kf , where Kf = nKf. The n
is calculated by the method of Schwarzenbach7 This
calculation gives the relative concentrations of the partially
deprotonated chelant species as a function of pH. The stability
constants become much lower in the acidity range commonly
encountered in spent acid fluids. For example, the stability
constants for Fe(III) with ethylenediaminetetraacetic acid
(EDTA) and nitrilotriacetic acid (NTA) at pH3 become log
14.5 and log 6.46 respectively. The same comparison with
Fe(II) shows a decrease in stability to log 3.73 and log 0.55.

SPE 54721

CHALATING AGENTS IN SOUR WELL ACIDIZING: METHODOLOGY OR MYTHOLOGY

Log Kf and Log Kf values

ion
EDTA EDTA(pH3)
Fe(III)
25.1
14.5
Fe(II)
14.3
3.73

NTA
15.9
8.8

NTA(pH3)
6.46
0.55

This constitutes a reduction in stability of ca. 8 to 10 orders

of magnitude. Fe(II) and NTA gives a value <log 1! This
suggests that NTA, under these conditions, will not protect
Fe(II) from undergoing deleterious reactions in the fluid
system. The above suggestion will be verified by experiment
(vide supra).
Complexes of NTA and EDTA
Preparation of the complexes of interest is essential for the
purpose of determining important properties such as solubility
and thermal stability under realistic conditions. The common
way of preparing complexed ions usually involves dissolution
of a metal salt and chelating agent at low pH followed by
addition of base (caustic) to increase the pH to 7 or greater.
Isolation is difficult because of water removal and salt
contamination.
A simple method to produce pure, isolable complexes for
study has been found. The procedure involves using Icelandic
Spar crystals, an aqueous medium, and a chelating agent. For
example, excess large single crystals of Icelandic Spar are
immersed in a measured quantity of water. The chelating agent
is then added in small aliquots. Carbon dioxide will slowly
evolve as the active protons of the chelating agent spend on
the carbonate. After gas evolution ceases, the procedure is
repeated. At some point the solubility product of the calcium
complex will be exceeded and precipitation will occur. The
precipitated solid can then be filtered and excess Spar crystals
removed. Washing the solid with alcohol and acetone and then
air drying (ca. 100C) completes the workup. This technique
produces very pure complexes as well as allowing the
solubility of the complexes to be calculated. Also, this
procedure readily accommodates other fluids such as 20%
calcium chloride water to simulate spent 15% HCl.
The calcium complex of NTA was prepared using the
above method. Analysis of the solid showed the molecular
formula to be: Ca(HNTA)2H2O. This material showed a
solubility of 240 and 72.5 lbs./Mgal in water and 20% CaCl2
respectively. Next the solubility of the complex was
determined at elevated temperature. A saturated solution of the
complex in 20% CaCl2 was heated in a pressure cell equipped
with a glass observation port. When the temperature reached
204F, massive precipitation occurred. The amount of
precipitate was not quantitatively determined. A qualitative
estimate would be that most of the complex was released from
solution at this temperature.
The EDTA analog was prepared using a similar procedure.
This complex showed excellent solubility (ca. 500 lbs. /
Mgal), far exceeding the solubility of free EDTA that will
dissolve in the treatment fluid. This salt also lost solubility at
elevated temperastures (240F).

Fe(II) complexes of NTA and EDTA were prepared by

spiking the initial 20% CaCl2/Icelandic Spar reaction mixture
with a known quantity of Fe(II) prepared from anhydrous
FeCl2 and deoxygenated 20% CaCl2 water. In the case of the
NTA, only when the quantity of NTA added to the system
exceeded BOTH the amount of Fe(II) and Ca ion did any
precipitation occur. The precipitate was identified as the
calcium complex. Clearly, the Fe(II) complex formed
preferentially. Surprisingly, the EDTA complex showed less
solubility than the corresponding calcium complex as
determined by the precipitation point. Iron depletion studies
showed the onset of complex precipitation occurred when 68
lbs./Mgal of EDTA had been consumed. Therefore,
Fe(II)EDTA solubility is quite low. 68 lbs./Mgal should be
considered to be the maximum concentration of EDTA in
stimulation designs for acidizing.
As predicted, these
solutions were extremely oxygen sensitive, instantly turning
blood red with introduction of air.
Thermal Stability of EDTA complexes can they survive?
The thermal stability of ferrous EDTA in 20% CaCl2 water
was explored. A cloudy solution of the complex (slightly
green due to oxidation) was heated under 500-psi nitrogen
pressure. The test solution remained unchanged until the
temperature had reached 250F. At this point, the solution
became both clear and colorless. The latter indicates that
reduction of trace quantities of Fe(III) had occurred. After a
period of 6 hours, the reaction vessel was cooled to ambient
temperature and slowly depressurized. Vigorous gas evolution
occurred during the latter stages of depressurization. Control
experiments using nitrogen and CO2 atmospheres in the
absence of the iron complex did not show this behavior. This
result highly suggests that the complex underwent thermal
decomposition, generating carbon dioxide in solution.
A similar experiment was carried out using the calcium
salt of EDTA. After two hours at 250F, the vessel was cooled
and depressurized. Again, vigorous gas evolution occurred
during the latter stages of the depressurization procedure.
Thus, both iron and calcium EDTA complexes appear to
decompose under these conditions. This result puts an upper
limit to the successful use of this chelating agent somewhere
below 240F.
Therefore, solubilities and thermal stabilities for the
complexes are not encouraging with respect to staying in
solution or successfully stopping hydolysis reactions (hence,
precipitation).
Reactions of Fe(II) Complexes with H2S at pH3
The above preparation now allows a definitive determination
to be made regarding the complex stability in the presence of
hydrogen sulfide.
Solutions of Fe(II) NTA and Fe(II)EDTA in 20% calcium
chloride water were prepared as described above. The pH of
the solutions was adjusted to a value of 3 using dilute HCl and
a pH meter. Marble chips were added followed by addition of
anhydrous hydrogen sulfide via a gas dispersion frit. Within

M. BREZINSKI

10 minutes, both samples had formed copious quantities of

black precipitate, which was analyzed as FeS. A white film of
organic material was found floating on the top of the samples.
This material was not analyzed but surely must be the fully
protonated chelating agent formed by a proton transfer. I.e.,
Fe(HNTA) + H2S

FeS + H3NTA

(1)

These crucial experiments show that neither chelating agent

will be effective in preventing FeS deposition under these
conditions (spent acid).
The NTA Precipitation Cycle an example
The following example serves to show how the experiments in
this document may come together and allow a system to be
better understood.
NTA is frequently used for iron control in sour well
environments. This particular chelating agent shows
tremendous solubility in strong acid fluids (>300 lbs./Mgal)
Also, the ferrous complex is more soluble than the calcium
complex. These properties appear to give the material an
advantage over EDTA. However, evidence presented in this
paper shows NTA (or EDTA for that matter) cannot
encapsulate enough coordination sites on Fe(II) at fluid pH
values below 2 to stop FeS formation. Also shown has been
the loss of solubility of the calcium complex at ca. 200F. The
increased solubility of NTA over EDTA is explained by
protonation forming the conjugate acid of the compound. This
acid has a pKa of <1 and will deprotonate when the acid
strength is reduced to a range of about 2% to 0.5% residual
HCl. At this point, free NTA only possesses meager solubility
(20 lbs. /Mgal at 65F, 60 lbs./Mgal at 160F, and 150
lbs./Mgal at 200F so most of the material will precipitate
from the fluid. Next, NTA will spend on the formation
forming a calcium salt. If the temperature is greater than about
200F, this complex will again form a precipitate. If on the
other hand there is Fe(II) in the system, the Fe(II)NTA
complex will form. However, the iron complex will react with
H2S and form FeS and free NTA, which will return to the
cycle. The end result will be (for a well over 200F): all FeS
will precipitate and all NTA will precipitate as a calcium
complex.
Experimental Precautions
Aqueous Fe(II) is exceedingly oxygen sensitive and must be
handled under rigorously anaerobic conditions. Schlenkware,
vacuum lines, and either a nitrogen or argon atmosphere are
essential to obtain meaningful results. FeCl24H2O is more
often than not, significantly contaminated with Fe(III). This
contamination is readily observed upon inspection of the
crystalline solid or aqueous solution of the salt. The partially
oxidized condition will result in a green tint to the solid or
solution. Pure aqueous Fe(II) is colorless even at
concentrations of >50,000 PPM. Also, the ion becomes a
stronger reducing agent upon chelation. This is the result of
pushing more electrons into an already oxidatively unstable

SPE 54721

metal center. This causes Fe(II) complexes to be even more

unstable than the hydrated ion. Hence, bubbling air through a
solution of Fe(II) EDTA causes an immediate color change
from colorless to deep red. Indicating formation of Fe(III)
EDTA.
Conclusions
1. The FeS damage mechanism allows FeS precipitation to
occur at significantly lower pH values than predicted
using simple equilibrium calculations. Consideration of
the formation as an active participant in all downhole
chemistry may give better insight into actual fluid
behavior in well stimulation treatments.
2. Chelating agents appear to be unable to prevent
precipitation of FeS under realistic downhole conditions.
3. Calcium complexes of certain chelating agents exhibit
reverse solubility properties with temperature and may
precipitate at relatively low temperatures.
4. The tested complexes of chelating agents decompose at
temperatures as low as 250F setting a low upper
temperature limit for use.
5. From these results, it appears that the only course
available to prevent FeS formation is to remove the other
product from the fluid namely H2S with the use of an
efficient hydrogen sulfide scavenger.
References
1.
2.
3.
4.
5.
6.
90

Crowe, C.W., Maddin, C.M.: U.S. Patent No. 4,574,050 (1987).

Dill, W.R., Walker, M.L., Ford, W.G.F.: U.S. Patent No.
4,679,631 (1987).
Crowe, C.W.: U.S. Patent No. 4,633,949 (1987).
Dill, W.R., Walker, M.L.: U.S. Patent No. 4,888,121 (1989).
Handbook of Analytical Chemistry, Meites, L. ed., 1st ed., New
York, McGraw-Hill, 1963.
Cotton, F.A., Wilkinson, G.: Advanced Inorganic Chemistry,
3rd ed., New York, Interscience, 1972.
Schwarzenbach, G. and Biedermann, W.:Helv. Chim. Acta.
31,331(1948).

Acknowledgement
The author would like to Halliburton management and thank
Marten Buijse of Halliburton European Research Centre for
his help in preparing this paper.

TABLE 1"L"*45"Ka Values vs FeS Precipitation

Point
-C3
-C4
R*"XCNWG,<

TGH0"5
;Z32/:
3Z32/34
30;

TGH07
8Z32/:
3Z32/37
504

,""ECNEWNCVGF"XCNWG"HQT"RTGEKRKVCVKQP"QH"(G5

TGH0"8
3Z32/9
3Z32/39
5098

SPE 54721

CHALATING AGENTS IN SOUR WELL ACIDIZING: METHODOLOGY OR MYTHOLOGY

TABLE 3- FeS Precipitation Test with Formation

Material in Spent Acid vs pH

TABLE 2"L FeS Precipitation Test

in Spent Acid vs pH
%QORQUKVKQP"QH"VGUV"HNWKF
(G*+++"EQPE0<
7.222"22/
*45"EQPE0<
5CVWTCVGF
(NWKF<
42'"%C%N4"YCVGT

Composition of test fluid

(G*+++"EQPE0<
7.222"22/
*45"EQPE0<
5CVWTCVGF
(NWKF<
42'"%C%N4"YCVGT
(QTOCVKQP<
%C%15"EJKRU"CFFGF"VQ"VJG"CDQXG
OKZVWTG

R*
2
3
4
5
6

R*
2
3
4
5

QDUGTXCVKQP
PQ"TGCEVKQP
PQ"TGCEVKQP
PQ"TGCEVKQP
PQ"TGCEVKQP
FCTMGPGF
UQNKFU"HQTOGF

QDUGTXCVKQP
ICU"GXQNWVKQP
ICU"GXQNWVKQP
EJKR"EQXGTGF"YKVJ"(G5
EJKR"EQXGTGF"YKVJ"(G5

1.0
0.9

2-

fractional composition

0.7

3-

H2 EDTA

0.8

4-

H EDTA

EDTA

H4 EDTA

0.6
0.5
0.4
0.3
0.2
-1

H3 EDTA

0.1
0.0
0.00

2.00

4.00

6.00

8.00
pH

Fig 1- Fractional Composition of EDTA Species vs pH

10.00

12.00

14.00