Enhancing Acid Stimulation Efficiency and Sustainability:

T he Role of Chelating Agents in Simulation Applications, the

alternative solution of conventional HCl stimulation.

Insight By:
Ibrahim Abdellatif, PhD in Petroleum Engineering
Ibrahim.Abdellatif1@outlook.com
Published on LinkedIn: December 2023
Publisher: Production Enhancement Group – PEG03

The primary objective of well stimulation operations is to enhance hydrocarbon recovery by increasing the flow
of hydrocarbons from the reservoir to the wellbore. This can be achieved through various strategies, such as
bypassing near-well pore damage and opening a flow path, especially in Sandstone, shale, mixed formations, or
carbonates/high carbonate content formations. One method involves creating a preferential flow path known as
wormholes, developed during the injection of fluids.

This article focuses on the utilization of chelating agents in Acid Stimulation treatments. There have been recent
challenges with conventional HCl-based fluids in acid stimulation, with negative impacts often outweighing the
benefits. These challenges include environmental and health impacts, damage to downhole tools, and formation
damage. Consequently, some regions restrict or limit the use of HCl as a stimulation fluid. To comply with
regulations and promote sustainability, researchers are compelled to seek quick alternatives.

Recently, researchers in service companies or operator labs have introduced so-called "green fluid solutions,"
primarily based on chelating agents. This article will highlight one promising and developed solution that
involves the use of a chelating agent as an efficient alternative to conventional HCl fluids.

Chelating agents, when used as the base fluid in well stimulation applications, offer several advantages, including:

▪ Low environmental impact.

▪ Non-corrosiveness to downhole equipment compared to HCl-based fluids.
▪ More efficient stimulation fluid solutions, leading to a higher regain permeability factor compared to
traditional acids and contributing to improved well productivity.
▪ Higher temperature range application.
▪ Simple design with optimal fluid volume.
▪ Fewer compatibility issues with downhole well fluids (workover fluids, heavy oils, high saline water, H2S-
containing wells).
▪ Lower etching, resulting in a slower reaction rate and deeper penetration into the formation (creating
branched wormholes in carbonates).
▪ Common chelating agents in oil and gas stimulation fluids include citric acid and amino polycarboxylic acid
products like EDTA. This article does not delve into the chemistry but provides insight into application
features. For any chemistry-related questions, feel free to reach out directly.

Taking EDTA (ethylenediaminetetraacetic acid) as an example of a common chelating agent, services companies
often use EDTA derivatives with different codes, although the working mechanism is nearly the same with minor
differences.
Using the fluid baseline of EDTA as an example, a 0.01Molar solution has a pH of 7 and medium thermal stability
(70-120 degC). Fluid engineers can design a fluid to extend the EDTA range to cover higher pH environments and
create an efficient fluid tailored to specific well conditions.

EDTA pH (0.01 M Solution) Therma stability rang

2Na-EDTA 4.0 -6.0 60-80 degC
3Na-EDTA 5.0 -7.0 75-100 degC
4Na-EDTA 10 -11 110- 125 degC
Questions to discuss:

➢ Why EDTA derivatives thermal stability increases with the increase of the metal ions?
➢ Does the EDTA thermal stability change with the metal ion change?
➢ How fluid engineer can extend the thermal stability of the overall fluid and extend the application, such as in
Hot Wells stimulation, HPHT Stimulation, Geothermal Applications.
➢ Example of Stimulation fluid design:

A client possesses an offshore oil well perforated in a carbonate formation dominated by carbonated formation
(Calcite 60%- dolomite 30% and Siderite 10%). The temperature at the top of the perforation stands at 110°C.
This well, drilled in 1970, exhibits promising reservoir parameters and offset data, indicating a significant
potential for increased production.

The well yields 0.5 tons of low API oil with a 20% gas cut and no water influx. The client seeks stimulation for the
open interval, specifically 20 meters in clusters, using a non-HCl fluid solution. How can such a fluid be designed
for this case?
**The fluid formulation proposed here is solely for illustrative purposes and does not represent the optimal design. It serves as a demonstration for this specific case. If you are
seeking the most effective formulation for this scenario or any other challenges, please feel free to contact me. I am available for further discussion and collaboration.

The base fluid on that case is recommend to be 4Na-EDTA, fluid overall pH will be round pH 11, the solubility of
calcite could reach to 80-90%, slower reaction rate with dolomite (wormhole paths that enhance the fluid flows),
chelating with siderite and avoid Iron ions precipitation and secondary formation damage.

Question to discuss:

➢ How to prepare practically the 4Na-EDTA fluid, and what is the optimum volume solution per each one meter
of perforation?
➢ How we can calculate the reaction rate, the optimum socking time? shutting time after treatment? flow back
procedure?
➢ What is the best injection rate, how is the expected Pressure behavior?

Follow me in the upcoming articles to get answers for the above questions, you are welcome to reach out if any
related questions.

➢ In the context of reservoirs stimulation, a wormhole refers to a preferential flow path that develops during
the injection of fluids (e.g., water or chemicals) into a porous rock formation, particularly in carbonate
reservoirs. Wormhole can occur due to variations in rock permeability, dissolution, or other factors.
➢ The formation of wormholes can have both positive and negative effects on hydrocarbon flow:
▪ Positive Effects:
o Enhanced Sweep Efficiency: Wormholes can improve the sweep efficiency of injected fluids,
helping to displace hydrocarbons from the reservoir matrix.
 o Improved Recovery: In certain cases, the creation of wormholes can enhance oil recovery by
providing more efficient pathways for fluid flow.
▪ Negative Effects:
o Channeling: Wormholes may channel the injected fluids through specific paths, potentially
bypassing significant portions of the reservoir. This can lead to uneven sweep and reduced overall
recovery.
o Early Water Breakthrough: Rapidly created wormholes might lead to premature breakthrough of
injected water in production wells.

Questions for Discussion:

❖ Why does the thermal stability of EDTA derivatives increase with the rise in metal ions concentration?
❖ Does the thermal stability of EDTA change when there is a variation in metal ions?
❖ How can fluid engineers enhance the overall thermal stability of fluids, extending their application in
processes such as Hot Wells stimulation, HPHT Stimulation, and Geothermal Applications?

Example of Stimulation Fluid Design:

A client owns an offshore oil well perforated in a carbonate formation dominated by Calcite (60%), Dolomite
(30%), and Siderite (10%). The temperature at the top of the perforation is 110°C. Despite being drilled in 1970,
the well exhibits promising reservoir parameters, suggesting significant potential for increased production. The
well yields 0.5 tons of low API oil with a 20% gas cut and no water influx. The client seeks stimulation for the
open interval, specifically 20 meters in clusters, using a non-HCl fluid solution. How can such a fluid be designed
for this case? *

**Note: The fluid formulation proposed here is for illustrative purposes only and does not represent the optimal design. It serves as a
demonstration for this specific case. For the most effective formulation for this scenario or any other challenges, please feel free to contact me
for further discussion and collaboration.

The short answer for the complex condition is:

The recommended base fluid for this case is 4Na-EDTA, with an overall fluid pH of around 11. The solubility of
calcite could reach 80-90%, ensuring a slower reaction rate with dolomite, creating wormhole paths that enhance
fluid flow. Chelating with siderite helps avoid iron ion precipitation and secondary formation damage.

Questions for Discussion:

❖ How can the 4Na-EDTA fluid be practically prepared, and what is the optimum volume solution per meter of
perforation?
❖ How can the reaction rate, optimum soaking time, shutdown time after treatment, and flow back procedure
be calculated?
❖ What is the best injection rate, and how is the expected pressure behaviour?

Follow us in upcoming articles to find answers to the above questions. Feel free to reach out with any related
inquiries.