The precipitations of the scales on the internal surfaces of the pipelines, surface facilities, and downhole equipment cause a lot of operational problems and, in severe cases, this might lead to shutting down the well. In the daily operation reports, scale deposition is very common and is a nightmare for the production and process engineers. The main problems of the scale depositions are a reduction in the inner diameter of the production tubes, reduction in the well production and pressure, surface and subsurface equipment failure, perforations, and formation damage in the reservoir [
1,
2,
3,
4]. The wettability of the reservoir rock could be changed due to the deposition of iron sulfide [
5]. Not only the production wells suffer from the scale, but even the water source wells, injection wells, and disposal wells have scale depositions [
5,
6]. The scale was deposited on the sand face and plugged part of the formation pores and, therefore, it will reduce the well productivity or the well injectivity in the case of production or injection wells [
7,
8,
9].
Sulfate and sulfide mixture scales are considered to be common scale types in the oil and gas production due to the different minerals and brines that coexist in the production stream, reservoir formation water, and injected water in the petroleum reservoir. Formation water in the reservoir and seawater is an important source for the brines, as it is used for injection operations to enhance reservoir recovery. Formation water contains sulfate ions with low concentrations, and calcium, and barium with high concentrations, while seawater contains sulfate ions with high concentrations and barium and calcium ions with low concentrations. Therefore, the incompatibility between the two types of water sources will lead to a scale forming as barium sulfate and calcium sulfate [
9]. Pyrrhotite (Fe
7S
8), troilite (FeS), mackinawite (Fe
9S
8), pyrite (FeS
2), marcasite (FeS
2), greigite (Fe
3S
4), sphalerite (ZnS), galena (PbS) are different sulfide scales. Hydrogen sulfide gas is considered as a common source of sulfides. Sulfates as scales are usually precipitated in the oil and gas fields as gypsum (CaSO
4.2H
2O), anhydrite (CaSO
4), barite (BaSO
4), hemihydrate (CaSO
4.5H
2O), celestite (SrSO
4). Sulfide scales are deposited when hydrogen sulfide reacts with minerals such as iron, zinc, and lead due to the incompatibility of brines. There are important factors that control the scale deposition, such as operating temperature and pressure, the chemical reaction equilibria, pH, exposure time for interactions, evaporation, and ionic strength [
10]. Barium sulfate-, calcium sulfate-, and strontium-based scales are the most common scale types in the oil and gas fields, in addition to oxides and hydroxides (Fe, Mg), carbonates such as (Ca, Mg, Fe), and sulfides (Fe) [
11,
12]. The most common sulfide scale is iron sulfide. The locations of scale depositions differ due to temperature and pressure conditions. Lead and zinc sulfide scales are found to be deposited in the shallower part of the well completion, control valves, and in the subsurface safety control valves [
13,
14]. Sulfate scales were found to be deposited by the seawater injection operations, and such a scale is one of the hardest scales to be removed as it has low acid-solubility. The incompatibility of different water sources is the reason behind sulfate scale deposition [
15]. The barium sulfate scale is also one of the most common scales in the petroleum industry, as barium sulfate is one of the drilling mud additives as a weighting material. Mud invasion into the drilled formation will carry the barium sulfates, depositing them in the formation pores that cause formation damage and permeability reduction [
16]. Calcium sulfate scale is found to be precipitated around the electrical submersible pump in the well and also in the reservoir zone [
17,
18]. Strontium sulfate was commonly related to the surface facilities of oil production. The main source of the strontium sulfate scale is seawater, which contains strontium ions in its mineral composition [
19].
Scale Removal
Scale removal in the oil and gas field is a difficult and complicated operation. Chemical dissolvers and mechanical removal are usually used together to remove the deposited scales. the design of the scale dissolver method should consider economic and technical aspects. It should be low-cost, non-damaging to the surface facilities, well tubed, equipped, and contain reservoir rock. In addition, it should have a high degree of thermal stability, be environmentally friendly and should not produce H
2S gas after scale dissolution [
20,
21]. The scale treatment cost is considered to be very high, especially if it stops oil and gas production [
22]. Therefore, scale inhibitors are considered to be an efficient way to reduce or prevent scale formation and the scale inhibitors have a wide application in oil fields. Scale inhibitors succeeded in preventing the formation of different types of scales [
9,
23,
24]. The success of the scale inhibitor function to prevent scale formation depends on the design of the inhibitor’s composition, the dose, and its efficiency under the operating pressure and temperature conditions. An inefficient design for the scale inhibitors will lead to scale deposition and the use of the scale dissolver to remove the scale precipitations [
25]. BinMerdhah et al., [
9] stated that the scale might be deposited due to mixing incompatible brines, pressure and temperature change, or the evaporation of brines.
Formulating a chemical dissolver to remove such scale types is a very difficult task due to the variety of minerals that exist in the same well. The reason for that is the different chemical reactions between the dissolver and the different scale minerals. Many types of scales are water-soluble, such as sodium chloride, while there are acid-soluble scales, such as calcium carbonate, iron sulfide, and iron oxide [
4]. Another challenge in the removal design is pH control. Calcium and barite sulfate scales removal are not dependent on the brine pH, however, the scales such as iron sulfide and carbonate depositions depend on the brine pH. Calcium sulfate has lower solubility at low-pressure conditions, and is less soluble in a dissolver solution with a high pH [
26].
Chemically, many organic and inorganic chemicals are commonly used for scale removal in the oil and gas fields. The chemical composition of the existing scale is a very important factor for the dissolver design [
27]. In the real field scales, a hydrocarbon layer coats the scale body and prevents the acid from contact with the scale and, therefore, surfactants are usually used to solve this interaction matter and enhance the scale–dissolver interactions.
Hydrochloric acid (HCl) is the most common acid used for scale removal in the petroleum industry [
28]. However, using HCl for scale removal cannot dissolve many scale types, expensive, corrosive, and generates toxic gas H
2S and therefore other additives must be added to control the reaction [
5,
29,
30,
31]. HCl can dissolve zinc sulfide [
32], and few iron sulfide scales as troilite and pyrrhotite; however, pyrite and marcasite are difficult to dissolve with HCl [
31]. Sulfate scales such as barium, calcium, and strontium sulfates were found to have low HCl acid-solubility [
22,
33].
Acetic acid, formic acid, maleic acid, and citric acid are different types of organic acids and they are used for scale removal for high-pressure, high-temperature (HPHT) reservoirs instead of HCl [
34,
35,
36]. However, the organic acids have a lower dissolution efficiency than HCl [
35], they are less corrosive and have a long-time reaction. Chelating agents are considered to be an alternate solution to organic and inorganic acids for the removal of scale from formations.
Another common scale dissolver is the chelating agents, which are a more environmentally friendly solution, and less corrosive [
37]. The most commonly used chelating agents are ethylenediaminetetraacetic acid (EDTA), hydroxyethyl ethylene diamine tetraacetic acid (HEDTA), hydroxyethyl iminodiacetic acid (HIDA), glutamic acid di-acetic acid (GLDA), diethylenetriamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), and methylglycinediacetic acid (MGDA). Studies were performed to provide a scale dissolver using the chelating agent for the pyrite iron sulfide scale with more than 80% pyrite, the chemical formulation for the dissolver contained 20 wt. % DTPA at pH 11 with 9 wt. % potassium carbonate as a catalyst. The formulation succeeded at dissolving the scale with an efficiency of 85% at a temperature of 70 °C for 48 h [
38,
39]. Nitrilotriacetic acid (NTA) is one of the chelating agents used for scale removal, and it has a biodegradability level higher that EDTA and DTPA [
40].
The pH has a great effect on the scale treatment process. The acids that are used for scale removal with a lower pH will greatly affect the well tubular integrity and increase the corrosion rate. The treatment design has recently been used to target the green scale removal with a basic pH to protect the surface facilities and downhole equipment from damage [
41,
42]. The combination of EDTA with tetrakis (hydroxymethyl) phosphonium salts (THPS) was studied to provide a scale dissolver with high pH and that helped to reduce the corrosion rate and the amount of corrosion inhibitor that is usually added to the removal solution [
42]. Ramanathan et al., [
43] studied the effect of pH control and treatment time on the chelating agent. The study determined the optimum pH and time of treatment for the removal of iron sulfide scale.
The objective of this paper is to introduce a novel non-corrosive dissolver to remove sulfate and mixed sulfide scale. The novelty in the new proposed non-corrosive dissolver is its high pH value with a very low corrosion rate, less than the acceptable limit by the oil and gas industry, based on the recent studies, to provide a basic pH scale dissolver. In addition, the new dissolver efficiently provided a high dissolution efficiency for the scale at a low-temperature condition of 45 °C.