SPE 157467

Improved Health, Safety and Environmental Profile of a New Field Proven

Stimulation Fluid

W. Braun, C.A. de Wolf, AkzoNobel, H.A. Nasr-El-Din, Texas A&M University. All SPE
Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the 2012 SPE Russian Ooi & Gas Exploration & Production Technical Conference and Exhibition held in Moscow, Russia, 16-18 October, 2012

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Acidizing treatments can help significantly improve the productivity of a well. Safe handling of commonly used corrosive
acids, however, is a significant challenge to properly manage during the execution of the treatments. The additives, such as
corrosion inhibitors, iron control agents, etc., typically used to mitigate the corrosive impact of acids and other un-wanted
reactions during the treatments adds to the complexity of safe handling, while further aggravating the environmental impact
of the overall treatment. Higher dosages of additives that are needed at higher treatment temperatures and pressures further
compound the challenge. With the industry needs trending to high temperatures & pressures, and stricter health, safety &
environmental (HSE) considerations, an alternative stimulation fluid that is suited for all the challenging conditions and be
globally applicable with an acceptable environmental profile would be ideal.
Recent studies and field applications with a new stimulation fluid based on glutamic acid diacetic acid (GLDA) has
shown that GLDA can improve permeability in carbonate and sandstone formations even at tough field conditions and can
maintain the integrity of wells made of various tubular metallurgies. In the present paper the health, safety and
environmental profile of GLDA is reviewed and compared against conventional stimulation fluids such as hydrochloric acid,
acetic acid, hydrofluoric, etc., along with the commonly used additives.
GLDA is to a large extent based on a natural amino acid made from sustainable resources. It is biodegradable in both
fresh and seawater. GLDA has a very favorable eco-tox profile and very low toxicity levels. In contrast to other stimulation
fluids and frequently used additives, GLDA does not have any hazard classification and therefore requires no adverse safety
labeling. GLDA can be handled easily and safely in the field with just standard chemical handling precautions in place.
Overall, GLDA is a safe, environmentally friendly and effective stimulation solution that can help improve productivity of a
well with the least possible well integrity or HSE concerns.

Introduction
The highest priority for any industry is to ensure the health and safety of the public and its workers. Safety is particularly
important for the extractive industries, like the oil industry, because workers exposed to the high risks of working in confined
area, on remote offshore platforms, or in other extreme environments. The public could be exposed to health and safety risks
from emissions from the operations, failure of impoundments, spills, and contamination of water sources (Arscott et al,
2012). Public concerns about the oil and gas industry, coupled with amplified media coverage of the industry practices, have
increased considerably in recent years. In terms of this ongoing discussion, the chemicals and techniques employed in the oil
field, together with their HSE profile, play a vital and increasingly important role for operators and service companies with
respect to their perception to the public (Sinanan et al.2005, Bradish et al. 2008).
The oil and gas industry has been using acid treatments as a method to increase productivity of wells for over a century.
With extraction getting more and more difficult and wells being drilled ever deeper, reliable stimulation technologies become
even more crucial to the industry. That said, stimulation treatments represent a real challenge to the oil industry due to
various reasons. One of the reasons is the difficulty of safely handling the corrosive and hazardous acids and treatment fluids
used for stimulation treatments. From the early commercial use up until now, hydrochloric acid (HCl) has remained the
primary acid for stimulation of carbonate formations, whereas mixtures of hydrochloric acid and hydrofluoric acid (HF)
became the standard in sandstone acidizing (Nasr El Din et al. 2012b). Increased number and higher dosages of additives
such as corrosion inhibitors, intensifiers, iron control agents, etc., that are needed at higher treatment temperatures and
pressures further compound the safe handling and eco-tox profiles of the overall treatment. Due to these trends, along with
permanently tightening HSE considerations, the industry has long sought to mitigate the potential hazard of the fluids
2 SPE 157467

employed.

GLDA and it applicability as a Stimulation Fluid

Glutamic acid diacetic acid, GLDA, is an organic acid and a chelate molecule, thus having the dual ability to function as an
acid in dissolving minerals such as calcium carbonate and as a chelant in keeping metal ions such as iron from precipitating.
Recent studies and field applications with a GLDA have proven that GLDA is capable to improve permeability in carbonate
and sandstone formations across wide field conditions while maintaining the integrity of well tubular made of low carbon
steel or chrome based metallurgy.
Mahmoud et al. (2010; 2011) extensively examined the use of GLDA for the stimulation of both carbonate and sandstone
formations. They have shown that GLDA can effectively form wormholes in calcite and dolomite without face dissolution or
washout, in contrast to 15% HCl. Secondly, they concluded that GLDA performs better in carbonate formations than other
chelating agents such as hydroxy ethyl ethylene diamine triacetic acid (HEDTA) and ethylene diamine tetra acetic acid
(EDTA) or weak organic acids such as acetic acids. Finally, they found that GLDA can effectively increase the permeability
of sandstone reservoirs without destabilizing clays, in contrast to HCl or HEDTA (Mahmoud et al 2011). Detailed evaluation
of the corrosive behavior of GLDA has shown that GLDA is gentler to carbon steel, chrome or duplex metallargies than
alternative stimulation fluids such as HEDTA, acetic acid, citric acid, formic acid etc (Nasr El Din et al 2012b, de Wolf et al,
2012).
A field application case study with GLDA revealed that GLDA based stimulation fluid was able to improve productivity
of the well significantly above conventional treatments (Nasr-El-Din et al 2012a). Multiple prior treatments with
conventional acids failed to improve productivity of the well, making the well a candidate for fracturing. Yet the treatment
with GLDA turned out to be very successful, acheiving a production enhancement of 110%, which was above the original
treatment target of 60% best case improvement expected by the operator and close to the expected fracturing result (Fig. 1).
The main objective of this paper is to evaluate the health, safety and environmental profile of GLDA. In addition, the
paper compares the safety and hazard classification of GLDA with other commonly used acids and the additives.

HSE Profile of GLDA

GLDA is based on a naturally occuring amino acid backbone, glutamic acid. The manufacturing process of GLDA involves
bio-chemical conversion of sugar beet waste to a strong chelating agent. Its natural origin contributes to its green nature and
renders GLDA biodegradable. The Bra Miljöval protocol established by the Swedish Society for Nature Conservation
certifies that 86 wt% of the GLDA molecule is based on renewable resources. It also possesses a small eco-footprint. Eco-
efficiency analysis has revealed that it is the most environmentally benign chelating agent of the group examined in that
study (Borén et al, 2009). The study analyzed the ecological impact of various products and evaluated the weighted
environmental impact of each product. When comparing GLDA against the traditional chelating agents, such as EDTA,
NTA, etc., it was revealed that GLDA in fact has the smallest eco-footprint in terms of its weighted ecological footprint, with
only half as high as the other chelants investigated in the study (Fig. 2).
The green and environmentally benign features of the GLDA molecule have a positive effect on its decomposition
behavior in free nature by being biodegradable. As Fig. 3 depicts, GLDA is readily biodegradable in fresh water and it is
inherently and ultimately biodegradable in sea water.
As to the hazard potential of a chemical, its toxicity to marine organisms and fish is an important factor. Several studies
have confirmed that GLDA imposes no risk to the marine environment and has extremely low aquatic toxicity. Table 1
higlights the low toxicity level tested for GLDA on various fishes and aquatic organisms. Moreoever, studies have confirmed
that GLDA is not an irritant, not mutagenic, nor genotoxic and does not inhibit the respiration due to contact.
GLDA is supplied and used in the field at pH 3.5 - 4, which makes it mild and very easy to safely handle the product even
in extreme conditions. On the whole, GLDA has no hazard classifications and carries no safety warnings. Because of its
inherent biodegradable and very low toxic nature, GLDA is allowed for use world wide without restrictions, even in areas
with stringent environmental regulations like the North Sea basin.

HSE Aspects of Conventional Treatment Fluids

There are mainly two different categories of acids employed nowadays in acidizing treatments, with the first group being
inorganic mineral acids like HCl, HF and mixtures thereof, and second group consisting of milder organic acids like formic
and acetic acid including chelate molecules at moderately low pH values, allowing them to both act as acids as well as metal
sequestering agents (Kalfayan 2008, Fredd et al. 1997, Huang et al. 2003). Most of these traditional fluids, however, do not
possess a favorable eco-tox and environmental profile. HCl and HF are highly acidic acids and can cause severe skin burns
and eye damage. Hydrofluoric acid is particularly worse due to its high toxicity, where it can be fatal on inhalation,
swallowing and/or skin contact (Chemiekaarten 2012). Therefore extreme precautions must be taken while working with HF.
Owing to its low dissociation constant, HF as a neutral lipid-soluble molecule penetrates tissue more rapidly than typical
mineral acids. Because of the ability of hydrofluoric acid to penetrate tissue, poisoning can occur readily through exposure of
skin or eyes, or when inhaled or swallowed. Symptoms of exposure to hydrofluoric acid may not be immediately evident. HF
interferes with nerve function, meaning that burns may not initially be painful. Accidental exposures can go unnoticed,
delaying treatment and increasing the extent and seriousness of the injury.
SPE 157467 3

Alternative organic stimulation acids like formic or acetic acids are also, of course, inherently acidic by their nature and
therefore can also cause skin burns and eye damage. Additionally they are, in their more contentrated solutions, flammable
and have to be labelled accordingly (Chemiekaarten 2012). Even HEDTA, which can be used as a stimulation agent as well,
is an irritant, and is not readily biodegradable.

HSE Aspects of Corrosion Inhibitors, Intensifiers and Iron Control Agents

The need to use highly acidic acids in conventional stimulation jobs makes the use of corrosion inhibitors to protect the
valuable tubulars inevitable. A vast amount of chemical compounds is in use nowadays as corrosion inhibitors (Kalfayan
2008, Kelland 2009). Phenomenologically, they can be divided into two main groups: primary or secondary inhibitors,
depending on the mechanism they inherently follow to impose protection to the metal (electrochemically, film-forming, etc.)
and, more importantly, if they are chemically changed during the process or not (Fischer 1959). Arguably, the most important
representatives of these two types of corrosion inhibitors are long chain alkyl and aryl nitrogen compounds, very often
quaternized (quats), that interact with the metal surface on a molecular level, and acetylenic alkohols (alkynols), that form a
protective film that shields the metal surface from acid attack. On top of this, at temperatures above 200°F modern corrosion
inhibitors need to contain intensifiers in order to achieve an acceptable protective performance. Most of these intensifers
induce a chemically reducing power to the system, such as formic acid and metal iodides of potassium, copper or antimony.
Arsenic compounds have been abandoned in the meanwhile, for obvious reasons. Based on environmental and cost concerns
it is evident that the use of these compounds is not desirable (Frenier 1988).
The class of quats is per se intrinsically unsafe to water based life and marine organisms as they establish, at least in part,
a biocidal effect, among others represented by the long chain benzyl quats, which are being used as biocides and
disinfectants.
Alkynols are another prominent group of corrosion inhibitors that are widely applied. Yet they do not have the most
favorable environmental and toxicological profiles. The simplest specimen of this group of compounds, progargyl alcohol (2-
propyne-1-ol), for instance, is labelled flammable, corrosive, toxic and environmentally dangerous; certainly not the most
desirable combination of properties that one wishes to deal with on a stimulation job, especially not in remote areas or off-
shore, one may think of the use of hoses or coiled tubing, mixing and pumping activities. Owing to the fact that inhibitors
must function over a wide range of conditions, blends of quaternary ammonium compounds with acetylenic alcohols
comprise most of the acidizing inhibitor formulations in use nowadays (Frenier 1988).
The use of GLDA as a stimulation fluid instead renders the use of additional corrosion inhibitors as well as intensifiers
unnecessary for most metallurgies and well conditions. For certain types of duplex metallurgies, GLDA requires no corrosion
inhibitors or intensifiers up to 400oF. For chrome based tubular no corrosion inhibitors are needed up to 350oF, with higher
more extreme temperatures requiring maximum 0.5 vol% of a corrosion inhibitor (de Wolf et al, 2012). For carbon steel,
only 0.001 vol% of a corrosion inhibitor is needed even at 300oF.
Another class of compounds that is frequently found in stimulation mixtures are iron control agents, which are usually
chelating agents. Commonly used iron control agents are EDTA, ethylene diamine tetra acetate, which is not readily
biodegradable, and NTA, nitrilo triacetate, a chemical that is a suspected carcinogen. These agents need to be added in order
to prevent the iron ions, that are dissolved from the metal tubulars by the corrosive stimulation acid or from the formation
itself, from forming sludges with asphaltenes present and clogging the pores and pore throats of the porous formation matrix
by precipitation. This need becomes obsolete in the case of using GLDA as stimulation fluid instead, because GLDA itself is
a chelating agent that is capable of sequestering any possible iron in solution, next to other metals that might be present as
well.

Conclusions
GLDA is an effective stimulation fluid with an outstanding HSE-profile. It combines a number of relevant advantages that
become increasingly important to the oil and gas industry as safety, health and environmental regulations become ever more
strict. The key HSE attributes of GLDA are:
1. GLDA, for the bigger part, is based on a sustainable, renewable bio-based feedstock.
2. GLDA is biodegradable in fresh and seawater.
3. GLDA has the best in class eco-footprint of the most common chelating agents.
4. GLDA has low toxicity levels in general and especially towards aquatic life and marine organisms.
5. GLDA does not have any hazard classification and can be handled easily & safely in the field.
6. GLDA is an effective stimulation fluid that needs no or vey low amount of additivies such as corrosion inhibitors or
iron control agents

Acknowledgements
The authors would like to thank AkzoNobel for supporting this project and for permission to publish this paper.
4 SPE 157467

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SPE 157467 5

Production Rate
300

(% of original  production)
250
Improvement 
200

150

100

50

0
pre‐treatment post treatment  Result with GLDA  expected 
target 20wt% fracturing result

Fig. 1—Production Rate improvement in a recent field application with GLDA

0.7
Resources
Weighted envrionmental impact

0.6 Energy consumption

0.5 Global warmingpotential

Photochemical ozone
0.4 creation potential
Acidification potential
0.3
Water emissions

0.2 Toxicity

Risk potential
0.1
Land use
0
GLDA EDTA NTA

Fig. 2—Comparison of the weighted ecological footprint of GLDA versus typical chelating agents in terms of the eco-
efficiency on equal weight basis.
6 SPE 157467

100
readily biodegradable in fresh
water

Biodegradability [%] 80

60

40 inherently and ultimately

biodegrabable in seawater

20

0
0 7 14 21 28 35 42 49 56 63
Time [days]

Fig. 3—Biodegradability behavior of GLDA in fresh and seawater.

GLDA
Rainbow Trout LC50, 96h
Daphnia Magna EC50, 48h
Green Algae EC50, 72 h

Table 1— Toxicity study of GLDA on various aquatic life forms