SPE 151740

Pushing the Limits: HT Carbonate Acidizing

O.E. Jimenez Bueno, G.R. Ramirez, Pemex; M.A. Quevedo Z., J.T. Resendiz Torres, F. Tellez Cisneros,
Schlumberger

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium and Exhibition on Formation Damage Control held in Lafayette, Louisiana, USA, 1517 February 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
The Mexico South Region produces more than 520, 000 bopd1 from mature carbonate reservoirs. These reservoirs have
widely varying reservoir pressures, presence of natural fractures and temperatures up to 350 degF. The extremely high
temperatures makes even more challenging the stimulation process with conventional systems resulting in excessive
corrosion and very inefficient wormholing.
An innovative solution, considering a chelating agent as treating fluid, has proved to be an effective approach to stimulate
these reservoirs. The post treatment production in two different wells showed outstanding results with higher rates than
previous treatments and the trend of the production declination was smoothed. This new stimulation solution aided with a
good candidate selection has led it to be the preferred solution for HT wells.
Well A was treated with 15.0 m3 of the fluid based on chelating agents as main system, with a solvent preflush and
overflush. Previous to this job two stimulation treatments were performed pumping a mixture of conventional acid systems.
In both occasions the production increased, however, the production declined to pre-treatment rates in a matter of days. When
treated with the new solution the production increased 254 bpd with almost no decrease with time (monitored for three
months), indicating a more efficient stimulation treatment, and greatly improved on the economical indicators.
Well B was stimulated with 20.0 m3 of chelating agent fluid after three previous attempts using conventional systems. The
production increased 726 bpd. Post-treatment behavior was the same as well A.
Wells A and B showed an increased production of 1.7 KBD with a very limited production declination because of more
efficient wormhole creation due to retarded reaction rates allowing a wide contact with the reservoir thus improving
production performance, Np and eliminating post-treatment neutralization and testing surface equipment requirements.
Introduction
As in the rest of the world, in Mexico, most of the easy-to-extract oil has been found. Recent price increases have led to oil
exploration in areas where extraction is much more expensive, such as in extremely deep wells, extreme downhole
temperatures, and environmentally sensitive areas or where high technology will be required to extract the oil. A lower rate
of discoveries per explorations has led to a shortage of drilling rigs, increases in steel prices, and overall increases in costs
due to complexity.
Specifically for Mexico South Region, the oil and gas production come primarily from carbonate reservoirs, which consist
mostly of calcium carbonate and dolomite formations, and almost 520, 000 bopd2 come from this kind of formations.
However, in terms of the oil industry, carbonates can be difficult to produce because of their varying degrees of

Barrel of Oil Per Day

Barrel of Oil Per Day

SPE 151740

permeability, their wettability, their susceptibility to fractures and finally, and nowadays more common, high pressure and
high temperature of the formations treated.

Although the fluids based on chelating agents technology are not new stimulation fluids used in the oilfield industry, neither
in the Mexico South Region, its characteristics allowed to provide a new option to stimulate HT3 carbonate formations,
obtaining better results after the stimulation based on this system than the ones obtained with previous acid treatments
performed with conventional acids, like HCl or organic acids. This paper will describe how by stimulating specific wells with
a chelating agent as the main fluid, their daily production not only increased but also kept constant for a longer period. These
kind of stimulations were designed due to the necessity to find a new alternative to effectively stimulate the wells, increase
daily oil production, optimize clients resources available and at the same time to use an already existent technology but with
a completely different scope.
Chelating agents are widely known in the oil industry as main components of scale removal and/or prevention systems,
however one of the properties of the chelating agents, in terms of stimulation fluids composition, is their ability to prevent
solids precipitation from the by-products of secondary reaction products as the acid spends while reacting with the formation.
For the specific case of the stimulation fluid used in the treatments described in this document, the main chelating agent used
in the formulation is an ethylenediaminetetraacetic acid (EDTA) which is used not only for scale removal but also as iron
precipitation control.
Some scientists had proposed different uses for different chelating agents. For the EDTA-type applications as primary
dissolution agents had been proposed and this is the fundament of the project: the use of a stimulation fluid based mainly on
EDTA as the primary stimulation system for carbonates formations acidizing. Due to the high bottomhole temperatures
present in the South region of Mexico, hydrochloric acid (HCl) is not enough efficient for the wormhole creation process, it
reacts almost immediately with the carbonate formation creating only a face dissolution reaction. Therefore systems based on
chelating agents were a perfect option for an optimal wormhole creation as they are slower-reaction solutions.
Problem Setting
The year 2010 hadnt been as good as the client expected in terms of production. In January, the oil production for the
Operative Unit where this project took place was 172,000 bpd, while four months later, in May, the production was 158,000
bpd. It means that the production dropped 20% and it was only half year. As the oil production target by the end of 2010 is
200 KBOPD in February of this year the acid stimulation activity went up. The National Oil Company required from the
service companies to perform more efficient stimulations jobs and with less delay.
After every acid treatment the flowback fluids must be neutralized, until they have a minimum pH of 5, prior to enter client
facilities, therefore testing surface equipment is a must in the location. Once the activity started to increase, Testing Services
was overloaded and surface equipment availability start to become an issue. This fact not only meant that the operations that
involved acid systems were delayed or cancelled, but also that more production was lost while the well was closed until the
flowback fluids met the pH requirements. That implied money lost (production hold up) and money wasted (testing
equipment and neutralization costs) for the client.
Reservoir Description
The Cretaceous carbonate platform extended throughout the south of Mexico has two known platforms, Yucatan Platform
to the southeast and Artesa - Mundo Nuevo Platform to the west. The typical facies from these environments are present as
shallow-water carbonates, slope facies including flow facies from the platforms known as brecchas and deep marine facies.
The Cretaceous has been subdivided into three distinct units, namely the Lower Cretaceous (KI), Middle Cretaceous (KM)
and Upper Cretaceous (KS). The producing reservoirs are of Upper Cretaceous to Upper Jurassic Kimmeridgian and
Thitonian.
The reservoirs in the south of Mexico for this areas produce medium gravity oil 36-40 API, the reservoir temperature ranges
go from 120 up to 180C, the dual porosity behavior reflects well during the production life, making clear the identification of
the fracture-dominated behavior from the matrix-fracture behavior and in most cases is followed by secondarily developed
gas cap and medium strength aquifers. The movement of the original fluids contacts is not uniform because of the reservoir
heterogeneities, fracture densities, vertical and lateral variation in permeability, fluid properties and exploitation rates.
3

High Temperature

SPE 151740

The problem of gas breaking throughout the wells is more relevant in those fields where nitrogen is injected at the top of the
structure for pressure maintenance purposes.
Water breakthrough is a serious problem in naturally fractured reservoirs; typically once water break into a well the water
production will rise and the oil production may drop to zero in a matter of weeks or even days.
Southern Mexico is characterized as an area where wells are deep, naturally fractured carbonate reservoirs, with depleted and
high pressure zones in the same reservoirs the wells are difficult to reach the drilled target and even more difficult optimized
the stimulation process to recover oil and gas production.
Carbonate reservoirs often have large and highly variable completion intervals, which can greatly complicate stimulation and
production operations. In many cases, these reservoirs exhibit marked vertical and lateral heterogeneity caused by
permeability barriers, natural fractures, and complex porosity distributions.
This study was developed based on acid stimulation jobs performed in the four main reservoirs of the South Region.
Formations where treatments were carried out are Kimmeridgian (Low, Middle and Upper) and the Upper Jurassic
(Oxfordian and Kimmeridgiense Tithoniense) which have the following characteristics:

Temp. (C)
Lithology

Porosity (%)
Matrix K (mD)
Fract. K (mD)
Pay zone (m)
Depth

Reservoir 1

Reservoir 2

Reservoir 3

Reservoir 4

130-170
40%Dolomite
50% Limestone
10%others
2-8
1-7
250 - 2000
20-50
5,000-6,500

130-150
80%Dolomite 15%
Limestone 5%others

175
20%Dolomite 70%
Limestone 10%others

90-160
20%Dolomite 75%
Limestone 5%others

3-6
1-4
20-200
20-60
6,500-7,000

2-5
0.5-3
30-100
10-100
4,000-6,000

10-20
1-12
50-5000
10-100
5,000-6,250
Table 1

One of the major challenges for the treatment of these formations, as we see in Table 1, is the temperature present in the area,
so conventional acids are not efficient enough to create deep penetration of matrix flow, reason why we look for an
alternative to stimulate oil and gas zones.
Project Development
Although the systems based on chelating agents are not new in the oilfield industry, neither in the Mexico South Region, its
characteristics allowed us to provide a creative, new and efficient way to stimulate HT carbonate formations, with excellent
results, minimizing the time that well be closed after the stimulation and therefore optimizing the production management for
the client.
It is known that the base of the systems with chelating agents in their composition is their efficiency in matrix stimulation
applications in HPHT carbonate formations. The particular system, foundation of this project, takes advantage of chelating
agents ability to chelate calcium, as well as iron, barium, and other metals by forming very stable coordination complexes in
aqueous solutions. However the most important characteristic of this fluid, in terms of the objective of this project, is that the
system has a pH of 4. Which important benefits this low pH property gives to dehydration oil process?
A. More efficiency than a normal acid job.
Chelating agents are very effective and efficient matrix fluids at high temperatures where HCl and organic acids have a high
reaction rate and have a low capacity to produce efficient wormholes at typical flow rates for most matrix treatments. Based
on comparisons of wormhole morphology, a solution of this fluid, based on chelating technology, used to stimulate limestone
at 350 F appears to be equivalent to 15% HCl used at 150 F and the same pumping rate.

SPE 151740

B. No neutralization post-treatment needed.

The system has a pH of 4 before it is pumped into the well. Once it is in contact with the formation the chemical reaction
begins and the more it react the more the pH of the fluid increase. This means that after the stimulation finished and the
stimulation fluids are flowed back to surface they have at least a pH of 5. This value is the minimum pH that the fluids must
have in order to get clients authorization to receive them in their facilities, so the neutralization process is avoided.
C. No testing surface equipment required.
As no neutralization of the fluids should be done after the stimulation treatment, there is no need of any testing equipment. It
doesnt matter if it is available or not, the stimulation job can be performed with no delay.
D. Earlier production
When the two activities mentioned in the points A. and B. are eliminated, the time it takes to the client to start producing the
well again, is considerable decreased. Instead of holding up the production for three days it will be hold up maximum eight
hours.4
Well Filtering and Candidate Selection
An exhaustive review was done initially in all producing wells located in the fields that constitute EL Castao. Wells
located in the fields Tecominoacn, Jujo, Jacinto, Paredn and Crdenas were analyzed in order to identify the one that will
be candidates for the project. The analysis included a reservoir evaluation and some operational aspects such as:

Number of intervals
Wells with two intervals as maximum were chosen. As the number of intervals increases the optimal collocation of the
fluids become more complex. As the stimulation is based in only one system the collocation of it has to be simple, with
no need of diverters.
Bottomhole Temperature
Almost all the wells located in the Tecominoacn, Jujo and Cardenas fields have more than 300 F as bottomhole
temperature, and the ones that have lower temperatures were eliminated as candidates.
Lithology
The chelating agent system is an efficient fluid stimulating HT carbonate formations. The basic lithology for this wells
are:
- Dolomite: 50-80%
- Calcite: 15-40%
Permeability
Wells which show no high permeability contrasts are the best candidates. In this region is common to find naturally
fractured reservoirs. In the case that one or the two intervals show a big contrast in permeability values it makes more
complex the stimulation job. Diverters will be required and will be necessary to neutralize it once it is flowback.

Once all these characteristics were reviewed well by well, the field Cardenas was the one that have more potential wells that
covered the minimum requirements to be stimulated only with the chelating agent system.
Execution and Evaluation
Wells A and B just to mention a couple of examples, were stimulated with this new technique in March of this year.
For the well A, 15.0 m3 of the fluid based on chelating agents were pumped as main stimulation system, with 5.0 m3 of nonreactive system, based on xylene as preflush and over flush. The production went from 633 bpd to 805 bpd. Previous to this
job, two stimulation jobs (identified with a red colour circle in the Figure 1) were performed by the competitor pumping a
mixture of organic acids, diverters and solvent systems. The results of these two jobs were an almost immediate increase in
production up to 1,000 bpd for the first job. Unfortunately the rate of declination of this production went down in just weeks.
After the second stimulation job performed by the competitor, the behaviour of the well production is pretty the same. Once
the well was stimulated with the chelating agent fluid the production not only increased 172 bpd but was stable for a longer
time. The trend of the rate of the production declination was changed completely. A more efficient stimulation was achieved.
4

Usually acid treatments last an average of five hours

SPE 151740

Four days later the well B was stimulated with 20.0 m3 of the chelating agent system. In this case the production went from
1,414 bpd to 2,140 bpd. Once again this well was stimulated previously by the competitor, exactly three times, with the same
kind of systems as the ones mentioned above. The production rate shows the same behaviour as in the case of the well A.
Lets analyze the case of a conventional acid treatment for the wells A and B. Each one will be closed around 12 hours for
the stimulation treatment and the neutralization of the flowback fluids would take two days approximately. That will make a
total of 2.5 days of hold up production for the client. If the well A has a production of 400 bopd, with 2.5 days without
receiving fluids into clients facilities, the production lost will be 1,000 barrels of oil, in the case of the well B, its production
is 1,078 bopd; meaning 2,695 barrels of oil lost. The lowest price for each barrel of oil this year was around $60 USD (in
March 2009); then if the client stopped producing 3,695 barrels of oil (for the two wells) it means a loss of $220,000 USD. If
we add the cost of the testing equipment, plus the neutralization operation and the production hold up costs, it will give a
total of $300,000 USD.
When the stimulation treatments are based on this system based on chelating agents, the time the production hold up is
reduced from 2.5 days to 0.5 days. The money that the client looses will be $44,000 USD against $300,000 USD. The cost
reduction will be of 85%.
With this kind of stimulations not only an increase and stabilization of the oil production was obtained, but an optimization
of the same production management was achieved by reducing the hold up production.This means a production and
economic improvement.
Conclusions
This paper presents the tree fundamental components, characteristics of chelating agent on stimulation treatments

A good understanding of the reservoir flow units and production mechanisms is essential to successfully perform
with chelating agent stimulations in wells with high temperature, production water an gas
The characteristics of certain stimulation ffluids based on chelating agents are not new in the oilfield industry, but
allowed to provide a new option to stimulate HT carbonate formations.
The efficiency in matrix stimulation applications in HPHT carbonate formations allowed to optimize several
processes such as:
-

More efficiency than a normal acid job

No neutralization post-treatment needed
No testing surface equipment required
Earlier production

SPE 151740

Acknowledgements
The autohors acknowledge the support and encouragement of PEMEX management for writing this paper ant their
permission to publish it.
References
1.

2.
3.

Ali, Husen, et al. Chelating Agent-Based Fluids for Optimal Stimulation of High-Temperature Wells, paper 77366
presented at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, 29 Septemeber 2
October 2002.
Aboud, Ricardo, et al. Effective Matrix Acidizing in High-Temperature Environments, paper 109818 presented at
the SPE Annual technical Conference and Exhibition held in Anaheim, California, U.S.A., 11-14 Novemeber 2007
Padilla y Sanchez,RJ Geologic Evolution of Southeastern Mexico from Mesozoic to the Present in the Regional
Context of the Gulf of Mexico Boletin de la Sociedad Geologica Mexicana, Vol LIX No 1 2007 pp 18-50 (Spanish
Version).