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Dissolvine StimWell - Brochure
Dissolvine StimWell - Brochure
Dissolvine StimWell - Brochure
Stimulation Solution™
AkzoNobel at a glance
AkzoNobel is proud to be one of the world’s leading
The production of oil and gas is being challenged by increasingly difficult conditions.
Extreme temperatures and high pressure, expensive metallurgy of the tubular,
extended reach wells and strict health, safety and environment regulations will dictate
the future of the industry. In many cases, conventional technologies no longer meet the
requirements of the oilfield engineer or regulatory bodies. With our ambition to deliver
Tomorrow’s Answers Today™, AkzoNobel has developed a unique stimulation fluid with
high thermal stability and low corrosion potential which is both effective and
environmentally-friendly. This brochure introduces and explains the many distinct
advantages of our Dissolvine® StimWell™ product.
5
Stimulation with hydrochloric acid (HCl) is a well Chelating agents, such as ethylene diamine
established technique to improve the production tetraacetic acid (EDTA), hydroxy ethyl ethylene
from a carbonate reservoir. HCl is effective in diamine triacetic acid (HEDTA) and nitrilo
the dissolution of calcium carbonate, the triacetic acid (NTA) also have a low corrosion
reaction products are soluble, it is readily potential and can effectively dissolve calcium
available and HCl in itself is cheap. At first sight, carbonate. But they have limited solubility and
HCl seems an ideal stimulation fluid, but HCl thermal stability under acidic conditions and
6 has many limitations that become even more suffer from slow biodegradability or an
problematic at downhole temperatures unfavorable toxicity profile. Many independent
exceeding 200°F. For example, HCl is corrosive, organizations have classified NTA as potentially
especially for chromium-based steel, it causes carcinogenic for humans and regulatory bodies
face dissolution and cannot prevent iron or are putting restrictions on the use of NTA in
asphaltene precipitation. To solve these (consumer) products.
problems, the application of HCl requires large
amounts of additives that make the treatment Sandstone reservoirs are generally treated with
as a whole very costly and increases the risk of hydrofluoric acid (HF) and HCl mixtures, also
creating formation damage rather than known as mud acid, to improve the permeability.
removing it. Although highly corrosive and very toxic, HF is
often used as it is the only chemical that can
Organic acids – such as acetic, formic or citric dissolve the siliceous material that sandstone
acid – eliminate some of these drawbacks as mainly consists of. The HCl is added to dissolve
they are less corrosive, give some iron control any carbonate damage and to control the
(citric acid) and reduce asphaltene sludge amount of damage due to numerous (re-)
formation. On the other hand, thermal precipitation reactions that are triggered by the
decomposition starts at 250°F and the solubility HF treatment. However, many sandstone
of the reaction products is limited, which formations contain clays – such as chlorite,
reduces the concentration of the fluids. Since kaolinite and illite – which are sensitive towards
these are weak acids, the reaction with HCl. Illite in particular has a tendency to break-
carbonate will never be fully completed and part up into small particles that can block the pores
of the acids will remain unreacted. As a of the formation, causing irreversible formation
consequence of these chemical properties, the damage. As a consequence of the complex
volumes and reaction time of an organic acid- chemistry between the mud acid and the rock,
based stimulation job are significantly higher. many sandstone acidizing treatments are
unsuccessful or even ruin the well totally.
3. The Perfect Stimulation Solution™:
Dissolvine® StimWell™
Berea
Bandera
2,0
Permeability (Kfinal/Kinitial)
Berea Bandera
1,5
Quartz 86 57
Dolomite 1 16
Calcite 2 -
1,0
Feldspar 3 -
Kaolinite 5 3
0,5 Illite 1 10
Chlorite 2 1
Plagioclase - 12
0,0
Figure 3:
Left: The inlet side of 9
a core after stimulation
with Dissolvine®
StimWell showing no
face dissolution.
Right: The inlet side of
a core after stimulation
with 15% HCl showing
severe face dissolution.
10
300 4
Permeability (Kfinal/Kinitial)
100 0
200 225 250 275 300
Temperature (˚F)
12
Pore volume to breakthrough (PV)
Figure 5: The
effectiveness of
10
Dissolvine® StimWell
compared with other
8
organic acids as
measured by core flood
tests with six-inch 6
Indiana Limestone at
250°F and 2 cm3 per 4
minute.
*d ata derived from 2
Huang et al (2003) SPE
82268 0
20wt% HEDTA, 10wt% acetic LCA*
pH=2.5* acid*
3.3. Iron control
The presence of iron, especially to remove. To tackle this problem, iron control agents such
ferric iron can cause numerous as EDTA, NTA, etc. are often added to the stimulation fluid.
problems in and near the wellbore. However, most of these chelating agents have limited
Ferric iron can originate from the solubility in acids and consequently provide little protection
formation itself, or more likely from against the detrimental effects of ferric iron. In contrast,
corroded tubular and even from Dissolvine® StimWell is highly soluble in most acids, as
contaminated stimulation fluids. shown in Figure 11 (page 20), and being based on a chelating
acid, it can effectively complex the ferric iron and keep the
It forms insoluble iron hydroxide iron in solution. It can therefore be added as an iron control 11
precipitates during acid treatments agent for most stimulation jobs.
when the acid gets spent and when
the pH rises above 2.5. Ferric iron Dissolvine® StimWell does more than just control iron alone.
also induces the precipitation of Figure 6 shows that the addition of Dissolvine®
asphaltenes, resulting in asphaltic StimWell improves the stimulation of a carbonate formation,
sludge which can block the whereas a treatment with HCl alone caused a reduction in
formation and thus reduce the permeability of more than 40%, due to the precipitation of
production from the well. In sour iron hydroxides. When Dissolvine® StimWell is used as a
wells iron ions are even more standalone fluid for the stimulation of carbonate or sandstone
challenging as they can form all reservoirs, there is no need to add extra iron controlling
sorts of insoluble iron sulfides, agents as it can do both jobs at the same time.
that – once formed – are difficult
100
Permeability change (%)
200˚F 40
300˚F
20
0
No iron
control
-20
-40
-60
3.4. Low corrosion
12
0,05
6-hours metal loss (lbs/sq ft)
0,02
0,01
0
200 250 300 350 400
Temperature (˚F)
1,0
6-hours metal loss (lbs/sq ft)
0,2
0.0009
0,0
Citric acid Acetic acid HEDTA Formic acid
15wt% 15wt% 20wt% 9wt%
13
Chromium steel
Compared with commonly used acidizing fluids,
Dissolvine® StimWell is extremely gentle
for chromium-based tubular, as illustrated in
Figure 8. At 300°F, Dissolvine® StimWell is
the only acidizing fluid that does not require a
corrosion inhibitor to keep the corrosion rate
over Cr-13 stainless steel below the maximum
value of 0.05 lbs/sq ft.
No corrosion inhibitors
Extensive corrosion studies have proved that
Dissolvine® StimWell has a remarkably low
corrosion potential for both low carbon steel and
chromium-based tubular. Figure 9 shows that for
some metallurgies, no inhibitors are required,
even up to temperatures as high as 400°F.
C1020 No Ci required
Low carbon steel
(G10200)
0.25 v% Ci A
0.50 v% Ci B
100 150 200 250 300 350
Temperature (˚F)
3.5. Safe for people and planet
+110%
200
150
Figure 11: Measured gas
production before and
100 after treatment with
Dissolvine® StimWell.
For comparison the
50
expected acidizing and
fracturing treatment
0
results are given.
pre- post expected
treatment treatment fracturing
target result
19
Dissolvine® StimWell:
Effective for carbonate and sandstone
Applicable over a wide temperature range (up to 400°F)
No or very low corrosion
Requires minimum additives
auses no formation damage
C
• no face dissolution
• prevents iron precipitation
• prevents sludge formation
• compatible with clays
Biodegradable
Safe and easy to handle
Cost effective
Product
Technical
Information
1. Product description
Dissolvine® StimWell™ is based on the recently developed
chelating agent glutamic acid diacetic acid (GLDA). As shown
below, GLDA has four carboxylic acid groups, giving it a powerful
acidic character, capable of dissolving calcium carbonate. In
combination with the nitrogen atom, these acid groups can also
form strong bonds with di- and trivalent metals, ensuring iron
and other metal ion control.
22
+
as supplied
* recommended concentration for carbonate stimulation
2. Chemical and physical properties
Dissolvine® StimWell
Dissolvine® StimWell HTF
50 50
40 40
30 30
20 20
10 10
23
0 0
25 50 75 100 125 EDTA NTA HEDTA GLDA
Temperature (˚F)
Figure 12: The viscosity as a function of temperature Figure 13: The solubility of various chelates at
of Dissolvine® StimWell HTF as supplied and as pH=3.4 and 70°F
50v/v% aqueous solution.
Viscosity Solubility
Viscosity is an important parameter for pumping Calcium carbonate is most effectively dissolved
and propagation of fluids into the well or under acidic conditions, in other words at low
reservoir and depends on concentration and pH. These conditions are also favorable for the
temperature. Figure 12 shows the viscosity of control of iron and, thus, the prevention of
Dissolvine® StimWell HTF and a 50v/v% dilution sludge. A highly concentrated acidic solution
as a function of temperature. of a chelating agent combines all these
functionalities and would therefore be a perfect
stimulation fluid. Figure 13 compares the
solubility of several chelating agents at pH=3.4
and shows the excellent dissolution properties
of GLDA under these challenging low pH
conditions. The unique properties of GLDA form
the basis for the unequaled versatility of
Dissolvine® StimWell in stimulation.
60
Solubility (wt% acid)
40 EDTA
NTA
HEDTA
30 GLDA
20
10
24
0
15% 28% 15% 28% 15% 28%
acetic acetic formic formic hydrochloric hydrochloric
acid acid acid acid acid acid
80
60
40
20
0
100 150 200 250 300 350
Temperature (˚F) 25
Thermal stability
The thermal stability of a stimulation fluid is of
utmost importance due to the increasingly high
reservoir temperatures. Figure 16 shows that
Dissolvine® StimWell is very stable up to at
least 350°F.
3. Environmental and toxicological data
A major advantage of Dissolvine® StimWell is its excellent
properties with regards to aquatic toxicity and environmental
acceptability. Dissolvine® StimWell is completely safe for the
environment and is permitted for offshore use around the world,
including the North-East Atlantic (OSPAR recommendation
2010/3) as can be seen in Tables 4 to 6.
26
Partitioning and bioaccumulation potential material, such as sugar beet waste. This natural
The N-octanol/water partition coefficient origin makes Dissolvine® StimWell a good basis
(Log Pow) has been determined by experiment for micro-organisms to feed upon, which is
(OECD 117) under the principles of Good confirmed by several biodegradability studies
Laboratory Practice (GLP). The result is listed under both fresh and seawater conditions.
in Table 4. In the OECD 306 Closed Bottle Test with sea
water, carried out in compliance with GLP, GLDA
Biodegradability was biodegraded 26 percent at day 28. In the
The main component of Dissolvine® StimWell is prolonged Closed Bottle Test, this substance was
GLDA, which is based on the natural amino acid biodegraded 83 percent at day 60. The
salt, mono sodium glutamate (MSG). MSG is biodegradation reached on the last day of the
produced by biochemical conversion of vegetable test demonstrates that GLDA should be
Table 4: The N-octanol/water partition coefficient Table 5: Biodegradability test data for Dissolvine®
(Log Pow) of Dissolvine® StimWell HTF StimWell HTF
Readily biodegradable Inherently and ultimately Figure 17: The biodegradation of Dissolvine®
biodegradable
80
StimWell determined by OECD 301D (fresh water)
and OECD 306 (sea water) tests.
60
Fresh water
Sea water
40
>20% at day 28
20
0
0 7 14 21 28 35 42 49 56 63 27
Time (day)
Organization Registered
US TSCA Yes
EC Yes
REACH Yes
OSPAR Yes*
29
Table 8: Labeling requirements for Dissolvine® StimWell versus conventional stimulation fluids under GHS*
HEDTA H319: C
auses serious eye irritation
• SPE 127923, Mahmoud, M., H.A. Nasr-El-Din, C.A. De Wolf, J.N. LePage, and J.H. Bemelaar:
Evaluation of a New Environmentally Friendly Chelating Agent for High-Temperature Applications,
SPE 127923, SPEJ: Vol 16, Issue 3, pp 559-574, 2011
• SPE 133497, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, J.N. LePage, Optimum injection rate
of a new chelate that can be used to stimulate carbonate reservoirs, SPE J online available,
hardcopy in press
30
Conference Publications
• SPE 131626, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, J.N. LePage, An effective stimulation
fluid for deep carbonate reservoirs: a core flood study (Beijing, China, 2010)
• SPE 132286, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, J.N. LePage, Stimulation of carbonate
reservoirs using GLDA (chelating agent) solutions (Port of Spain, Trinidad, 2010)
• SPE 139815, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, A.K. Alex, Sandstone acidizing
using a new class of chelating agents (Woodlands, TX, US, 2011)
• SPE 139816, A.I. Rabie, M.A. Mahmoud, H.A. Nasr-El-Din, Reaction of GLDA with Calcite:
Reaction Kinetics and Transport Study (Woodlands, TX, US, 2011)
• SPE 140149, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, A.K. Alex, Effect of Lithology on the
flow of chelating agents in porous media during matrix acidizing treatments (Oklahoma City, OK,
US, 2011)
• SPE 149127, M.A. Mahmoud, I.M. Mohamed, H.A. Nasr-El-Din, C.A. de Wolf, When should we use
chelating agents in carbonate stimulation? (Al-Khobar, Saudi Arabia, 2011)
• SPE 143086, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, A.K. Alex, Effect of reservoir fluid type
on the stimulation of carbonate cores using chelating agents (Macae, Brazil, 2011)
• SPE 143301, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, A.K. Alex, Novel environmentally
friendly fluids to remove carbonate minerals from deep sandstone formations (Noordwijk,
the Netherlands, 2011)
• SPE 147395, M.A. Mahmoud, H.A. Nasr-El-Din, C.A. de Wolf, Removing Formation Damage and
Stimulation of Deep Illitic-Sandstone Reservoirs Using Green Fluids (Denver, CO, US, 2011)
Contact us
For more information about Dissolvine® StimWell™ or our services, please contact us at
StimWell@Dissolvine.com, or any of our regional offices: