An Environmentally Friendly Stimulation

Fluid for High-Temperature Applications

J.N. LePage, SPE, C.A. De Wolf, SPE, and J.H. Bemelaar, AkzoNobel; and H.A. Nasr-El-Din, SPE, Texas A&M University

Summary
Matrix acidizing is used in carbonate formations to create flow
channels from the formation to the wellbore; in sandstone formations, however, the goal is to dissolve materials that impair well
performance. However, the use of acids in deep wells has some
major drawbacks, including high reaction rate and corrosion to
well tubulars.
We have discovered a new stimulation chemical that can be
used as a replacement for or in combination with acid treatments
in deep wells. A polyacid whose structure allows for acidification
is described. The polyacidic chelate L-glutamic acid, N, N-diacetic
acid (GLDA) is manufactured from L-glutamic acid (MSG). The
chelate-based fluid very effectively dissolves CaCO3, and it is less
corrosive to the equipment and easy to handle.
This paper discusses the reaction of the new chelate, GLDA,
with calcite and compares its performance with other available chelates, including ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid
(NTA), and ethanoldiglycine (EDG). GLDA dissolves calcite over
a wide pH interval, although it is less effective than HEDTA at
pH > 5. A unique property of GLDA is its high solubility; solutions
exceeding 40 wt% can be achieved at a pH of approximately 2,
whereas HEDTA solubility is limited to approximately 10 wt%.
A mole of GLDA with a natural pH of approximately 1.5 is capable
of dissolving up to two moles of CaCO3. Throughout the pH range,
GLDA appears to be as thermally stable as HEDTA.
As an additive to hydrochloric acid (HCl), GLDA is as effective
as HEDTA in preventing precipitation of moderate levels of Fe3+
in spent acids. At high Fe3+ concentrations, GLDA is slightly less
effective than HEDTA on a molar basis; but, to deal with high Fe3+
levels, GLDA may be better because significantly higher concentrations of it are possible in various acids. In 28 wt% HCl, HEDTA
has limited solubility while GLDAs solubility exceeds 40 wt%.
From an environmental standpoint, GLDA is readily biodegradable and is made from a renewable raw material, monosodium
glutamate. GLDA has low toxicity and aquatic toxicity characteristics. As a replacement for HCl, GLDA is significantly safer and
less corrosive.
Introduction
There are two principal means employed for solubilizing calcite scale
downhole: acidizing, which acts on carbonate, and chelation, which
acts on calcium ions (Ca2+). The most common means employed is
the use of mineral acid solutions, such as 15 wt% HCl and, to a lesser
extent, solutions of acetic and formic acids. Under acidic conditions of
pH < 4, the solubilization of calcite principally proceeds through protonation of carbonate/bicarbonate ions to CO2 by means of Eq. 1:
2H + + CaCO3 H + + Ca 2+ HCO13 Ca 2+ + CO 2 + H 2 O.
. . . . . . . . . . . . . . . . . . . . . . . . (1)
The Ca2+ salt of chloride (or the counter-ion of the acid used)
should remain soluble under the treatment conditions. A primary
advantage of HCl is its significant dissolving capacity for calcite,

Copyright 2011 Society of Petroleum Engineers

This paper (SPE 121709) was accepted for presentation at the SPE International
Symposium on Oilfield Chemistry, The Woodlands, Texas, USA, 2022 April 2009, and
revised for publication. Original manuscript received for review 23 February 2009. Revised
manuscript received for review 1 March 2010. Paper peer approved 8 March 2010.

104

whereby 1 gal of 15 wt% HCl can dissolve nearly 1.8 lbm of

CaCO3 (Frenier and Ziauddin 2008).
However, there are drawbacks to the use of strong and concentrated acids such as HCl, such as too rapid reaction in the vicinity
of the wellbore in addition to significant potential for corrosion
of iron components and subsequent mobilization of (temporarily)
solubilized iron salts. Both reaction rate and corrosion of well
tubulars are aggravated at higher downhole temperatures. Various
additives can be used to reduce corrosion, but the solubilization
of even small amounts of iron can lead to post-precipitation of
Fe(OH)3 (Crowe 1985; Taylor et al. 1999) or iron sulfide if H2S
is present (Nasr-El-Din et al. 2002). For this reason, iron-control
additives such as chelates are often used in conjunction with
acids. In addition, an H2S scavenger should be used in sour wells.
Addition of a suitable chelate in the live acid can delay/prevent
precipitation of Fe(OH)3 as the acid is spent and the pH rises above
pH 12 (Taylor et al. 1999).
Use of acids besides HCl, such as acetic and formic acids,
provides for a reduction in both reactivity and corrosion rate.
Unfortunately, the advantages of these acids are at the expense
of calcite-dissolving capacity. Because of the limited solubility of
calcium acetate and formate salts, the maximum concentrations
of acetic acid and formic acid that can be used are below 13 and
9 wt%, respectively. The dissolving capacity of these organic acids
is significantly less than that of 15 wt% HCl.
Because of the problems associated with strong acids, alternative dissolvers such as chelating agents have been explored. Just
as chelates are used with acids to prevent precipitation of iron by
complexation, they have been used also to dissolve carbonate and
sulfate scales in various fields, including fields in the North Sea and
the Gulf of Mexico (Jordan et al. 2000; 2006). Fredd and Fogler
(1998) were the first to examine the use of EDTA in stimulation of
carbonate formations. Frenier and coworkers have been advocates
on the use of chelates, particularly HEDTA, for dissolution of
calcite (Frenier et al. 2000; 2001; 2003; 2004).
The mechanism involved for calcite dissolution with EDTA (see
Table 1 for the structures of EDTA and other chelates used in the
present study) is given by
EDTA 4 + CaCO3 [ EDTA Ca ]

+ CO32,

. . . . . . . . . . (2)

where a complexation constant can be written as (Martell et al.

2003)
( EDTA Ca )2
= 5 1010 or log K = 10.7 .
K=
EDTA 4 Ca 2+

)(

. . . . . . . (3)

Chelates offer the benefit of lower reaction rates with calcite

and less corrosion potential because they are principally used at
higher pH values and can be chloride free. But, chelate solutions
provide significantly lower calcite-dissolving capacity than acids
because of the need to use 1 mole of chelate/mole of calcite. One
gallon of a 15 wt% solution of EDTA/Na4 has calcite-dissolving
potential that is one-fifth that of HCl.
Perceived problems in using chelates such as EDTA, HEDTA,
and NTA either as calcite dissolvers or as iron-control agents are
their environmental and safety characteristics. While considered
safe, EDTA and HEDTA are not readily biodegradable, although
various mechanisms exist in the natural environment to allow for
their eventual degradation (Bucheli-Witshel and Egli 2001). On the
March 2011 SPE Journal

TABLE 1CHELATE MOLECULAR WEIGHTS, PROTONATION CONSTANTS, AND METAL STABILITY CONSTANTS
Chelate
Abbreviation

Structure

pKa Values

Molecular Weight

L og K
Ca

2+

Fe

3+

Acid

Sodium Salt

pK1

pK2

pK3

pK4

EDTA

292

380

10.2

6.2

2.7

10.7

25.1

HEDTA

278

344

9.9

5.4

2.6

8.1

19.7

GLDA

263

351

9.36

5.0

3.5

2.6

5.9

11.7*

NTA

191

257

9.7

2.5

1.8

6.4

15.9

EDG

177

221

8.7

2.2

4.7

11.6

* Value is not listed in the National Institute of Sciences and Technology Standard Reference Database 46 version 7.0 for Critically Selected Stability Constants of Metal
Complexes. Experimental results indicate that the Fe3+ stability constant of GLDA is comparable to NTA.

other hand, while NTA is readily biodegradable, it is classified as

possibly carcinogenic to humans and, therefore, creates handling
and environmental-discharge concerns. Other chelates, such as
EDG [also known as hydroxyethyliminodiacetic acid (HEIDA)
(Frenier et al. 2003)], have been identified as readily biodegradable. However, EDG is more limited in its ability to control iron
and to dissolve calcite.
Blauch et al. (2003) first reported on the multifunctionality of
citric acid, whereby the acidity of citric acid protonates carbonate
and the citrate formed is capable of chelating Ca2+ and prevents
dissolved iron from precipitating. Citric acid is also readily biodegradable and offers low corrosion potential. A downside of citric
acid is the limited solubility of calcium citrate under certain conditions (Al-Khaldi et al. 2005, 2007). Also, the results of the first
field trials were below expectation, which was explained in terms
of low solubility of calcium citrate (Burgos et al. 2004).
Lactic acid (2-hydroxypropanoic acid) is similar to citric acid,
but the solubility of its calcium salt is high (Nasr-El-Din et al.
2007). An ester of lactic acid was used in an acid fracturing treatment in a carbonate reservoir. Analysis of well-flowback samples
did not show any evidence of calcium lactate. A full description of
this treatment was given by Nasr-El-Din et al. (2009).
While there are shortcomings in the use of chelateslimited calcite-dissolving capacity, slow biodegradabilitychelates play a vital
and growing role in stimulation fluids. The ideal chelate for stimulation, therefore, should offer environmentally friendly characteristics
in addition to multifunctionality (like citric acid) but with enhanced
solubility and chelation properties. One such material that has been
identified as having many of these positive attributes is GLDA.
GLDA is in the same class of chelating agents as EDTA, called
amino polycarboxylic acids (APCs), possessing a single central
nitrogen atom, as do NTA and EDG, whereas EDTA and HEDTA
both have two. The structure of GLDA is unique in that a major
portion of the molecule is derived from monosodium glutamate
(MSG), a flavor enhancer used in the food industry. MSG is principally made from the fermentation of readily available corn sugars
and is considered a renewable raw material.
On the basis of an extensive literature survey, current chelating
agents either have limited solubility in strong HCl acids or are not
environmentally friendly. We developed a new chelating agent,
which has the potential to be used in concentrated acids and as a
standalone stimulation fluid. The objectives of this study are to (1)
measure the solubility of GLDA in water and various acids, (2)
determine the ability of the new chelate to dissolve calcium and
chelate iron, (3) assess GLDAs biodegradation, and (4) examine
its stability and corrosion rates.
March 2011 SPE Journal

Experimental Procedures
Chelating agents EDTA, HEDTA, GLDA, NTA, and EDG (also
known as HEIDA) were obtained from AkzoNobel. Acetic and
formic acid, HCl, FeCl36H2O, and CaCO3 were obtained from
Fluka Chemical Company. Sodium hydroxide and CaCl22H2O
were obtained from J.T. Baker.
The solubility of GLDA in water was determined by acidifying
a GLDA/Na4 solution with HCl to various pH values. All GLDA
solutions contained greater than 40 wt% GLDA and remained clear
for at least 3 months at room temperature.
The solubility of the GLDA and the remaining chelates in
water or acids was determined by stepwise addition of the chelate
to the water or acid until an oversaturated solution was reached.
Subsequently, the solution was stirred for 48 hours and the concentration of chelating agent was determined by a complexometric/potentiometric endpoint titration using a ferric chloride solution
at pH = 3.
For the determination of the calcite-dissolving capacity, 30mL bottles with caps were filled with 25.0 mL of chelate solution
(2.5 mmol chelate) and a magnetic stirrer. Subsequently, CaCO3
(5 mmol) was added to the bottles. The bottles were stirred for 40
minutes and filtered off. The calcium concentration in the filtrates
was analyzed by flame atomic absorption spectroscopy.
The iron-control experiments used 25 g of a 15 wt% HCl solution that contained 2,500 and 25,000 ppm Fe3+ solutions prepared
from FeCl36H2O. Chelate acid was then added in an equimolar
ratio to the ferric ions. No chelate was added in the blank experiment. Subsequently, powdered CaCO3 was added portionwise (in
0.5- or 1-g increments) to the acidic solutions until a precipitate
was visible in one of the solutions. Equal amounts of CaCO3 were
added to the other solutions. The solutions were filtered after
24 hours, and pictures were taken of both precipitate and filtrate.
Biodegradation was determined using the closed-bottle test
described in the Organization for Economic Cooperation and
Development (OECD) 1992 Guidelines for Testing of Chemicals,
Degradation and Accumulation, Ready Biodegradability, Guideline
301 (van Ginkel et al. 2005).
The corrosion potential of GLDA solutions was tested on completely immersed coupons of cut low-carbon steel (SAE 1020) at
158F (70C) for 1 week under static nonaerated conditions. The
corrosion rate in mm/a was calculated on the basis of weight loss
of the coupons.
The thermal stability of the chelates was determined by heating
10 mL of a 0.1-M chelate solution in a 100-mL Teflon pressure
vessel for 4 hours at 149C (300F) or 177C (350F), using a
temperature-controlled microwave oven, resulting in a pressure
105

2+
Log Cond. Stability Constants Ca , log K'

12

10

EDTA
HEDTA

GLDA
4

NTA
EDG

10

12

14

pH
Fig. 1The calculated conditional stability constants (K) of various chelates with Ca2+ as a function of pH.

means to combine the thermodynamic complexation constants with

side reactionssuch as protonation of the chelatethat occur as
a function of pH. Fig. 1 shows a plot of log conditional stability
constants of these chelates as a function of pH. Expectedly, the plot
predicts the maximum strength of chelation of Ca2+ with APCs will
occur at high pH values, and full ionization of the APC will occur
when pH exceeds pK1 listed in Table 1. Note that complexation
of APCs with Fe3+ is more complex and maximum logK binding
occurs at pH of almost 3. LogK binding constants of GLDA fall
below the strong chelates EDTA and HEDTA, reside above EDG,
and are almost equal to NTA in the ability to complex Ca2+ and
Fe3+ at any pH value.

of 4.5 and 9 bar, respectively. The thermal stability was measured

in one series per temperature to avoid differences in the heating
profile. The stability was calculated from the chelate concentration before and after heating, as determined by complexometric/
potentiometric endpoint titration using a ferric chloride solution at
pH 3. The remaining solutions were analyzed by nuclear magnetic
resonance (NMR).
Results and Discussion
The chemical properties of APCs can be characterized by the
acid-dissociation constants and the stability constants for specific
metals ions. The acid-dissociation constants are listed in Table 1
as logKa or pKa. It is the pKa values that define the acidic nature
of these materials; the lower the pKa is, the more acidic or readily ionizable the acid is. As will be discussed later, the pKa value
when coupled with the solubility of the chelate influences which
salt types and physical forms of these chelates are available on a
commercial scale.
Table 1 also shows logK complexation constants of a number
of chelate products with Ca2+ and Fe3+. As described earlier, the
complexation constants define how a fully ionized APC (such as
EDTA4 or HEDTA3) associates with the free metal ion. The concept of the conditional stability constant K allows one to provide a

Solubility of Chelates
Fig. 2 shows the solubility of chelates over a wide pH range. It
is from such data that strategies on formulation stability of fluids
can be deduced. Additionally, the solubility profile affects what
commercial forms of these products are available. A common
property among the APCs shown is their solubility at high pH,
which is expectedly high because of the complete ionization of
the carboxylate groups. This is fortunate because the commercial
manufacture of APCs almost always starts with the production of
the sodium salts of chelates at high pH. Another shared solubility

60

Solubility, wt% as acid

50
40
EDTA
HEDTA

30

GLDA
NTA

20

EDG

10
0
0

10

12

14

pH
Fig. 2The solubility of various sodium chelates at 20C as a function of pH expressed as the weight percentage of the corresponding chelate acid. At pH < 4, the long-term solubility of GLDA is ensured up to 10 wt% as acid.
106

March 2011 SPE Journal

60

Solubility, wt% as acid

50
40

15% acetic acid

28% acetic acid

30

15% formic acid

28% formic acid

20

15% hydrochloric acid

28% hydrochloric acid

10
0
EDTA

HEDTA

GLDA

NTA

EDG

Fig. 3The solubility of APCs in various acids at 20C. The listed acid concentrations reflect the concentrations before dilution
with the chelate.

propertywith one exceptionis the rather low solubility at low

pH because of the protonation of these carboxylate groups, which
suppresses ionization of the chelate.
The poor solubility of EDTA at low pH clearly has its drawbacks in using EDTA in low-pH stimulation fluids. However, this
property does allow for efficient manufacture of two important
EDTA solid products that are used in the oilfield industry: disodium EDTA (solubility is approximately 10 wt% at pH 4.5) and
EDTA acid (solubility is approximately 0.05 wt% at pH 2). EDTA
can be readily converted to highly soluble ammonium and potassium salt solutions, both of which are used for descaling/completion, but they will behave like sodium salt when used in HCl
solutions. NTA acid is another material that is efficiently isolated
from simple acidification of the NTA trisodium salt solution.
While the solubility of HEDTA is also suppressed at low pH,
it does have a significantly higher solubility (approximately 1015
wt% at pH 23), a fact that has made Frenier and Ziauddin (2008)
advocates for the use of HEDTA in low-pH formulations. Note
that commercial HEDTA is limited to the approximately 40-wt%
trisodium salt solution at approximately pH 13.5, which needs to
be pH adjusted with HCl.
In Fig. 2, the notable exception to the generally low solubility
of APCs at pH 23 is GLDA, where the solubility exceeds 40 wt%.
Such high solubility makes it difficult to isolate the solid acid on

a commercial scale. However, the potential use of a concentrated

acidic fluid containing pure chelate for stimulation and other purposes is significant.
Fig. 3 shows a comparison of the solubility of these chelates
in HCl, formic acid, and acetic acid, where they might be useful
as iron-control agents. Both HEDTA and EDG offer considerable
solubility in 15 wt% HCl, but their solubility is significantly suppressed in 28 wt% HCl. NTA is moderately soluble also, while
EDTA has limited utility in these acidizing fluids. GLDA is a
notable exception, showing significant solubility in all the acids
examined. It is important to mention that a similar high solubility
of GLDA is also found in sulfuric, phosphoric, and nitric acids.
GLDAs high solubility under extremes in pH, high ionic strength,
and low free-water content offers great flexibility in its use in various oilfield applications (stimulation, scale removal, and cleaning
of drilling-fluid filter cake).
Dissolution of Calcite With Chelates
Fig. 4 shows the ability of chelates to dissolve CaCO3 over a range
of pH values. At pH 5 and greater, the dissolving capacity of chelate-containing fluids is principally driven by the chelates ability to
complex Ca2+. EDTA and HEDTA are both strong chelates for Ca2+
and show a near 1:1 molar efficiency in their ability to dissolve calcite. Less efficient for dissolving calcite are those with lower stability

Dissolution of CaCO3,
moles CaCO3 /mole chelate

EDTA

HEDTA
HEDTA,
Frenier

GLDA
EDG
0
0

10

12

Initial pH of Solution
Fig. 4The dissolution of CaCO3 with various chelates as a function of initial pH at 20C.
March 2011 SPE Journal

107

GLDA

HEDTA

Blank

Fig. 5Excess CaCO3 in spent HCl acid in the presence of 2,500 ppm Fe3+. GLDA and HEDTA give a nearly white precipitate
indicative of CaCO3 with low precipitated Fe(OH)3. The brownish precipitate in the blank solution without chelate is caused by
Fe(OH)3 precipitation.

GLDA

HEDTA

Blank

Fig. 6Excess CaCO3 in spent HCl acid in the presence of 25,000 ppm Fe3+. GLDA gives a slight orange precipitate caused by a
small quantity of precipitated Fe(OH)3, whereas HEDTA gives a nearly white precipitate indicative of CaCO3 with low precipitated
Fe(OH)3. The brown precipitate in the blank solution without chelate is caused by large quantities of Fe(OH)3 precipitation.

constants, such as GLDA, NTA, and EDG, even at pH 1112 where

their ability to complex Ca2+ is at a maximum (see Fig. 1).
At pH < 5, APCs initially behave as normal acids, and the
calcite is dissolved by a protonation reaction; but, when the acid
is spent, the chelate inside provides the means to complex Ca2+ or
Fe3+, preventing the deposition of the latter. As a result, chelates
such as GLDA that have high solubility at low pH can offer both
high calcite-dissolving power and chelation ability.
As shown in Fig. 4, a mole of GLDA/H3Na with a starting pH of
approximately 3.0 can dissolve approximately 1.5 moles of calcite,
whereas 1 mole of GLDA/H4 having a pH of approximately 1.5 can
dissolve up to 2 moles of calcite. Calculated on a per-gallon basis, a
20 wt% solution of these GLDA fluids can dissolve approximately
1.1 and 1.5 lbm calcite/gal, respectively. By contrast, the calcitedissolving capacity of a 20 wt% EDTA/Na4 (pH 12) or of 20 wt%
HEDTA/Na3 (adjusted to pH 2.5 with HCl) is 0.52 and 0.74 lbm
calcite/gal dissolved, respectively.
A more potent dissolution fluid for calcite can be obtained by
dissolving chelates in more-concentrated acids. Here, the principal
role of the chelate is to control and prevent Fe(OH)3 precipitation
as the pH of the spent acid increases. Figs. 5 and 6 show residual
CaCO3 filtered from the spent HCl solutions that contained 2,500
and 25,000 ppm of Fe3+, respectively. Where indicated, GLDA
and HEDTA were initially present in the HCl at the same molar
concentration as the Fe3+. Fig. 7 shows the filtrates from the 2,500ppm-Fe3+ experiment. The color or lack of color of the filter and
filtrate is directly related to the Fe+3 ion content. Expectedly, with
no chelate present (blank), Fe(OH)3 readily precipitates (dark color
of filter) with little to no soluble Fe present in the filtrates (colorless solution). However, as noted by the nearly white color of the
filter from the 2,500-ppm-Fe3+ test solutions, both the HEDTA and
GLDA are equally effective at keeping Fe(OH)3 from precipitating.
At a concentration of 25,000 ppm Fe3+, a small amount of Fe(OH)3
is observed in the spent HCl solution containing GLDA, whereas
essentially no Fe(OH)3 precipitate is formed with HEDTA. Clearly,
this latter condition is extremevery high Fe coupled with the
use of an exact stoichiometric amount of the GLDA. Under such
high Fe+3 conditions, an excess of GLDA would likely be needed
to reduce formation and precipitation of Fe(OH)3.
108

Biodegradation of Chelates
An important aspect of the use of chemicals in the oil field is
related to their environmental, health, and safety effects. The
replacement of highly reactive, corrosive, and volatile fluids
containing HCl with a nonvolatile chelate is highly advantageous.
A further favorable environmental characteristic of GLDA is that it
is readily biodegradable. Fig. 8 shows the degradation of GLDA in
fresh water vs. time in an OECD 301D test using unacclimated bacteria. After an induction period, the GLDA is shown to biodegrade
readily by achieving > 60% degradation within a 28-day period,
similar to what is found for NTA and EDG. Fig. 8 also shows the
general lack of degradation of HEDTA (similar to EDTA) under
these testing conditions.

GLDA

HEDTA no chelate

Fig. 7Filtrates of spent HCl acid in the presence of 2,500 ppm

Fe3+. The color in the chelate-containing acids is caused by complexed Fe3+ ions, whereas the lack of color in the blank filtrate
with no chelate indicates the absence of dissolved Fe3+ ions.
March 2011 SPE Journal

100

Biodegradation, %

80

60

40

20

0
0

10

20

30

Time, days
Fig. 8The percentage of biodegradation of GLDA () and HEDTA
() vs. time in OECD 301 D closed-bottle tests inoculated with
unacclimatized activated sludge. The dashed line represents the
pass level of the ready biodegradability test.

Stability and Corrosion Rate

To be effective, chelate fluids used for stimulation need to be stable
at high temperatures for several hours. Fig. 9 shows the percentage
of GLDA and HEDTA remaining after heating for 4 hours at 300
and 350F (149 and 177C, respectively). With the possible exception of a single data point at pH 1.5, the thermal stability of GLDA
appears to be on the same order as HEDTA. NMR analyses showed
that the major breakdown products of the chelates are formic acid
and cyclic GLDA or cyclic HEDTA, respectively. Under these
conditions, no precipitate was formed during heating.
The corrosion potential of GLDA solutions was tested [National
Association of Corrosion Engineers (NACE)] on completely
immersed coupons of cut low-carbon steel at 158F (70C) for
1 week under static conditions. The corrosion rate as mm/a was
calculated on the basis of weight loss of the coupons. A 40 wt%
solution of GLDA/H3Na at pH 3 resulted in a corrosion rate of
11.2 mm/a (0.3438 lbm/ft2 over a 1-week period) on the low-carbon-steel coupons. At lower temperatures and higher pH values,
significantly less corrosion to low-carbon steel was found. There
is a need to use a suitable corrosion inhibitor if GLDA is used at
high temperatures or used at low temperatures for a longer period
of time (more than a day). The same recommendation applies to
other chelates that are used at low pH values and high temperatures. More details on the solubility and use of GLDA for matrix
acidizing are given by Mahmoud et al. (2010).

Conclusions
On the basis of an extensive literature survey, current chelating
agents either have limited solubility in strong HCl acids or are
not environmentally friendly. We developed a new chelating agent,
GLDA, which has the potential to be used in concentrated acids
and as a standalone stimulation fluid. This new chelate offers significant advantages over conventional chelating agents:
It is a fairly good chelate for both Ca2+ and Fe3+ and offers high
solubility over a wide pH range; and, most significantly, aqueous
solutions of up to 40 wt% are possible at pH 2.
It is highly soluble in acids, even in 28 wt% HCl where HEDTA
solubility is limited.
The monosodium salt (pH 3) or free acid (pH 1.5) GLDA by
itself offers significant dissolving capacity for calcite.
It is as effective, or nearly as effective, as HEDTA in preventing
Fe(OH)3 precipitation in spent HCl acids.
GLDA is readily biodegradable vs. conventional chelates currently used in stimulation fluids.
Solutions of GLDA are less corrosive than HCl and will be safer to
handle. And, because high concentrations of GLDA are possible in
28 wt% HCl, the control of high levels of Fe should be possible.
From a manufacturing standpoint, we are actively developing
the process needed to manufacture GLDA-solution products having a low pH. Such products will be chloride free (having lower
corrosion potential) and will have a low sodium content and, thus,
will be more compatible with hydrofluoric-acid-based stimulation
fluids that are used in sandstone formations.
Acknowledgments
The authors wish to acknowledge AkzoNobel for granting permission to publish this paper and the contributions of coworkers Ingrid
Huybens, Kees van Ginkel, Martin Heus, and Arjen Reichwein.
The anonymous reviewers of this paper are acknowledged for
many useful comments.
References
Al-Khaldi, M.H., Nasr-El-Din, H.A., Blauch, M.E., and Funkhouser, G.P.
2005. New Findings on Damage Potential, Geochemical Reaction Mechanisms, and Production Enhancement Applications for Citric Acid. SPE
J. 10 (3): 267275. SPE-82218-PA. doi: 10.2118/82218-PA.
Al-Khaldi, M.H., Nasr-El-Din, H.A., Mehta, S., and Al-Aamri, A.D. 2007.
Reaction of citric acid with calcite. Chemical Engineering Science
62 (21): 58805896. doi: 10.1016/j.ces.2007.06.021.
Blauch, M.E., Cheng, A., Rispler, K., and Khallad, A. 2003. Novel Carbonate Well Production Enhancement Application for Encapsulated
Acid Technology: First-Use Case History. Paper SPE 84131 presented
at the SPE Annual Technical Conference and Exhibition, Denver, 58
October. doi: 10.2118/84131-MS.
Bucheli-Witshel, M. and Egli, T. 2001. Environmental fate and microbial degradation of aminopolycarboxylic acids. FEMS Microbiology
Reviews 25 (1): 69106. doi: 10.1111/j.1574-6976.2001.tb00572.x.

Chelate after Heating, %

100

GLDA
149C (300F)

80
177C (350F)
60

HEDTA

40

149C (300F)
20
177C (350F)
0
0.6

1.3

1.5

2.8

12.5
pH

0.6

2.1 12.3

Fig. 9The percentage of GLDA and HEDTA remaining after heating for 4 hours at 149C (300F) and at 177C (350F).
March 2011 SPE Journal

109

Burgos, G., Birch, G., and Buijse, M. 2004. Acid Fracturing With Encapsulated Citric Acid. Paper SPE 86484 presented at the SPE International
Symposium and Exhibition on Formation Damage Control, Lafayette,
Louisiana, USA, 1820 February. doi: 10.2118/86484-MS.
Crowe, C.W. 1985. Evaluation of Agents for Preventing Precipitation of
Ferric Hydroxide From Spent Treating Acid. J Pet Technol 37 (4):
691695. SPE-12497-PA. doi: 10.2118/12497-PA.
Fredd, C.N. and Fogler, H.S. 1998. Alternative Stimulation Fluids and their
Impact on Carbonate Acidizing. SPE J. 3 (1): 3441. SPE-31074-PA.
doi: 10.2118/31074-PA.
Frenier, W.W. and Ziauddin, M. 2008. Formation, Removal and Inhibition of Inorganic Scale in the Oilfield Environment, 63. Richardson,
Texas: SPE.
Frenier, W.W., Brady, M., Al-Harthy, S., Arangath, R., Chan, K.S., Flamant,
N., and Samuel, M. 2004. Hot Oil and Gas Wells Can Be Stimulated
Without Acids. SPE Prod & Fac 19 (4): 189199. SPE-86522-PA. doi:
10.2118/86522-PA.
Frenier, W.W., Fredd, C.N., and Chang, F. 2001. Hydroxyaminocarboxylic
Acids Produce Superior Formulations for Matrix Stimulation of Carbonates. Paper SPE 68924 presented at the SPE European Formation Damage Conference, The Hague, 2122 May. doi: 10.2118/68924-MS.
Frenier, W.W., Rainey, M., Crump, D.W., and Jones, L. 2003. A Biodegradable Chelating Agent is Developed for Stimulation of Oil and
Gas Formations. Paper SPE 80597 presented at the SPE/EPA/DOE
Exploration and Production Environmental Conference, San Antonio,
Texas, USA, 1012 March. doi: 10.2118/80597-MS.
Frenier, W.W., Wilson, D., Crump, D., and Jones, L. 2000. Use of Highly
Acid-Soluble Chelating Agents in Well Stimulation Services. Paper
SPE 63242 presented at the SPE Annual Technical Conference and
Exhibition, Dallas, 14 October. doi: 10.2118/63242-MS.
Jordan, M.M., Graham, G.M., Sorbie, S.K., Matharu, A., Tomlins, R., and
Bunney, J. 2000. Scale Dissolver Application: Production Enhancement
and Formation Damage Potential. SPE Prod & Fac 15 (4): 288295.
SPE-66565-PA. doi: 10.2118/66565-PA.
Jordan, M.M., Marlow, D., Johnson, T.L., and Johnston, C. 2006. The Evaluation of Enhanced (Carbonate/Sulfate) Scale-Dissolver Treatments for
Near-Wellbore Stimulation in Subsea Production Wells, Gulf of Mexico.
Paper SPE 100356 presented at the SPE International Oilfield Scale
Symposium, Aberdeen, 31 May1 June. doi: 10.2118/100356-MS.
Mahmoud, M., Nasr-El-Din, H.A., De Wolf, C.A., and LePage, J.N. 2010.
Evaluation of a New Environmentally Friendly Chelating Agent for
High-Temperature Applications. Paper SPE 127923 presented at the
SPE International Symposium and Exhibition on Formation Damage
Control, Lafayette, Louisiana, USA, 1012 February. doi: 10.2118/
127923-MS.
Martell, A.E., Smith, R.M., and Motekaitis, R.J. 2003. NIST Standard
Reference Database 46: Critically Selected Stability Constants of Metal
Complexes, Version7.0. Gaithersburg, Maryland: Standard Reference
Data Program, National Institute of Standards and Technology.
Nasr-El-Din, H.A., A.A. Zahrani, A.A., Garzon, F.O., Giraldo, C.A.F.,
Al-Hakami, I.M., and Al-Marri, H.M. 2009. Acid Fracturing of Gas
Wells by Use of an Acid Precursor in the Form of Solid Beads: Lessons Learned From First Field Application. SPE Prod & Oper 24 (2):
320335. SPE-110895-PA. doi: 10.2118/110895-PA.
Nasr-El-Din, H.A., Al-Humaidan, A.Y., Fadhel, B.A., Frenier, W.W., and
Hill, D.G. 2002. Investigation of Sulfide Scavengers in Well-Acidizing Fluids. SPE Prod & Fac 17 (4): 229235. SPE-80289-PA. doi:
10.2118/80289-PA.
Nasr-El-Din, H.A., Al-Zahrani, A., Still, J., Lesko, T., and Kelkar, S. 2007.
Laboratory Evaluation of an Innovative System for Fracture Stimulation
of High-Temperature Carbonate Reservoirs. Paper SPE 106054 presented at the International Symposium on Oilfield Chemistry, Houston,
28 February2 March. doi: 10.2118/106054-MS.
Taylor, K.C., Nasr-El-Din, H.A., and M. Al-Alawi, 1999. Systematic Study
of Iron Control Chemicals Used During Well Stimulation. SPE J. 4 (1):
1924. SPE-54602-PA. doi: 10.2118/54602-PA.
Taylor, K.C., Nasr-El-Din, H.A., and Saleem, J.A. 2001. Laboratory Evaluation of Iron-Control Chemicals for High-Temperature Sour-Gas Wells.

110

Paper SPE 65010 presented at the SPE International Symposium on

Oilfield Chemistry, Houston, 1316 February. doi: 10.2118/65010-MS.
van Ginkel, C.G., Geerts, R., and Nguyen, P.D., 2005. Biodegradation of
L-glutamate diacetate by mixed cultures and an isolate. In Biogeochemistry
of Chelating Agents, ed. B. Nowack and J. Van Briesen, Chap. 10, Vol. 910,
183194. New York: ACS Symposium Series, Oxford University Press.
James N. LePage is technical service and development manager for AkzoNobel Functional Chemicals chelate operations.
email: jim.lepage@akzonobel.com. He has more than 30 years
of experience in research and development and marketing of
chelating agents. In the past 5 years, LePages focus has been
directed to the areas of biodegradable chelates and the
use of chelates in the oil field. He holds a BS degree in chemistry from the University of Massachusetts and a PhD degree
in analytical chemistry from Northeastern University. LePage
began his career at WR Graces Hampshire Chemical division in Nashua, New Hampshire, during his college years and
became manager of Analytical R&D and Technical Service
laboratories while there. In 1997, he joined AkzoNobel when
it acquired Hampshires chelate business. LePage received
AkzoNobels 2008 Environmental Sustainability Award for his
work on chemical processing of oil field chemicals. Corine A.
de Wolf is a project leader at the research and development
laboratory of the AkzoNobel sub-Business Unit Chelates. email:
corine.dewolf@akzonobel.com. Her main fields of interest
include the functionality and properties of chelates in oilfield
applications, cleaning, micronutrients, and food fortification.
Previously, de Wolf worked at TNO, a Dutch research institute,
as a research specialist on parts and precision cleaning. She
holds an MS degree in chemistry from Utrecht University and a
PhD degree in heterogeneous catalysis and surface chemistry
from Leiden University, both in the Netherlands. She has contributed to two patents and 14 technical papers on various
subjects. Josine H. Bemelaar is an employee at the research
and development laboratory of the AkzoNobel sub-Business
Unit Chelates. email: josine.bemelaar@akzonobel.com. She
holds a BS degree from the Saxion Hogeschool Enschede in
organic chemistry. Bemelaars research interests are on the
properties and functionality of chelates. On this subject, she
was coauthor of two patents and a technical paper. Hisham
A. Nasr-El-Din is a professor and holder of the John Edgar
Holt Chair at Texas A&M University in petroleum engineering.
Previously, he worked for 15 years as principal professional
and team leader of the Stimulation Research and Technology
Team, Saudi Aramco. Before joining Saudi Aramco, he worked
for four years as a staff research engineer with the Petroleum
Recovery Institute in Calgary. He also worked as a research
associate with the University of Saskatchewan, the University
of Ottawa, and the University of Alberta. His research interests
include well stimulation, formation damage, cementing, drilling
fluids, two-phase flow, enhanced oil recovery, rheology, conformance control, interfacial properties, adsorption, and nondamaging fluid technologies. Nasr-El-Din has several patents
and has published more than 400 technical papers. He is an
adjunct professor with the University of Alberta and has supervised several MS and PhD students. He has received numerous awards within Saudi Aramco for significant contributions
in stimulation and treatment-fluid technologies and stimulation design and for his work in training and mentoring. NasrEl-Din holds BS and MS degrees from Cairo University and a
PhD degree from the University of Saskatchewan, all in chemical engineering. He serves on the SPE steering committees on
corrosion and oilfield chemistry, is a review chairperson for the
SPE Journal and is a technical editor for the SPE Production
& Operations and SPE Drilling & Completion journals. He was
invited to give keynote presentations in various SPE and NACE
conferences. He received the SPE Regional Technical Discipline
Award for Production and Operations in 2006, was named a
Distinguished SPE Member in 2007, and received SPE awards for
Outstanding Associate Editor (SPE Journal ) and Outstanding
Technical Editor (SPE Production & Operations) in 2008. In addition, he received SPE Production and Operations Award and
Outstanding Associate Editor Award (SPE Journal) in 2009.

March 2011 SPE Journal