Novel In-Situ Gelled Acid System Based on Inorganic Nanoparticles

Gelled acid systems based upon gelation of hydrochloric acid (HCl) are widely used in in both matrix acidizing and fracture acidizing treatments to prevent acidizing fluid leak-off into high permeable zones of a reservoir. The gelled up fluid system helps retard the acid reaction to allow deeper acid penetration for hydrocarbon productivity enhancement. The in-situ gelation is typically achieved by using crosslinked polymers with the acid. Conventional in-situ crosslinked gelled acid systems are made up of polyacrylamide gelling agent, iron based crosslinker and a breaker chemical in addition to other additives, with the acid as the base fluid. However, the polymer-based systems can lead to damaging the formation due to a variety of reasons including unbroken polymer residue. Additionally, the iron-based crosslinker systems can lead to scaling, precipitation and or sludge formation after the acid reacts with the formation, resulting in formation damage and lowering of hydrocarbon productivity. In this paper we showcase a new nanoparticles based gelled acid system that overcomes the inherent challenges faced by conventional in-situ crosslinked gelled acid systems. The new system can work in 5 to 20 % HCl up to 300°F. The new system does not contain any polymer or iron based crosslinker that can potentially damage the formation. It comprises nanoparticles, a gelation activator, acidizing treatment additives along with HCl. The new in-situ gelled acid system has low viscosity at surface making it easy to pump. It gels up at elevated temperatures and pH of 1 to 4, which helps with diverting the tail end acid to tighter or damaged zones of the formation. We demonstrate that the viscosification and eventual gelation of the new system can be achieved as the acid reacts with a carbonate formation and the pH rises above 1. As the acid further reacts and continues to spend there by increasing the pH beyond 4, the gel demonstrates reduction of viscosity. This assists in a better cleanup post the acidizing treatment. Various experimental techniques were used to showcase the development of the nanoparticle based acid diversion fluid. Static and dynamic gelation studies as a function of time, temperature and pH are reported. The gelation performance of the new system was evaluated at temperatures up to 300°F and discussed in the paper. Comparative performance of different types of gelation activators on the gelation profile of the nanoparticles is evaluated. It is also shown that the gelation and viscosity reduction is entirely a pH dependent phenomenon and does not require any additional breaker chemistry, and therefore provides more control over the system performance. The novelty of the new gelled acid system is that it is based upon nanoparticles making it less prone to formation damage as compared to a crosslinked polymer based system.

Impact of Delayed Flowback on Well Performance: Case Study

Due to a resource optimization and efficiency improvements, wells that are hydraulically fractured in the tight gas Barik Formation of the Khazzan Field in the Sultanate of Oman are often temporarily left shut-in directly following a large scale massive hydraulic fracturing stimulation treatment. Extensive industry literature has often suggested (and reported), that this may result in a significant direct loss of productivity due to the delayed flowback and the resulting fracture conductivity and formation damage. This paper will review the available data from the Khazzan Field address these concerns; indicating where the concerns should and should not necessarily apply. The Barik Formation in the Khazzan Field is an over-pressured gas-condensate reservoir at 4,500 m with gas permeability ranging from 0.1 to 20 mD. The average well after hydraulic fracturing produces 25 MMscfd and 500 bcpd against a wellhead pressure of 4,000 psi. A typical hydraulic fracturing stimulation treatment consists of 14,000 bbl of a borate-crosslinked guar fluid, placing upwards of 1MM Lbs of high conductivity bauxite proppant within a single fracture. In order to assess the potential production loss due to delayed flowback operations, BP Oman performed a suite of formation damage tests including core samples from the Barik reservoir, fracture conductivity considerations and dynamic behaviors. Additionally, normalized production was compared between offset wells that were cleaned-up and put onto production at different times after the hydraulic fracturing operations. Core tests showed a range of fracture conductivities over time with delayed flowback after using the breaker concentrations from actual treatments. As expected, enhanced conductivity was achieved with additional breaker. The magnitude of the conductivity being created in these massive treatments was also demonstrated to be dominant with respect to damage effects. Finally, a normalized comparison of an extensive suite of wells clearly showed no discernible loss of production resulted from any delay in the flowback operations. This paper describes in details the workflow and resulting analysis of the impact of extensive shut-in versus immediate flowback post massive hydraulic fracturing. It indicates that the impact of such events will be limited if the appropriate steps have been taken to minimize the opportunity for damage to occur. Whereas the existing fracturing literature takes the safe stance of indicating that damage will always result from such shut-ins, this paper will demonstrate the limitations of such assumptions and the flexibility that can be demonstrated with real data.

Minimizing Formation Damage in Drilling Operations: A Critical Point for Optimizing Productivity in Sandstone Reservoirs Intercalated with Clay

The recovery of oil and gas from underground reservoirs has a pervasive impact on petroleum-producing companies’ financial strength. A significant cause of the low recovery is the plugging of reservoir rocks’ interconnected pores and associated permeability impairment, known as formation damage. Formation damage can effectively reduce productivity in oil- and gas-bearing formations—especially in sandstone reservoirs endowed with clay. Therefore, knowledge of reservoir rock properties—especially the occurrence of clay—is crucial to predicting fluid flow in porous media, minimizing formation damage, and optimizing productivity. This paper aims to provide an overview of recent laboratory and field studies to serve as a reference for future extensive examination of formation damage mitigation/formation damage control technology measures in sandstone reservoirs containing clay. Knowledge gaps and research opportunities have been identified based on the review of the recent works. In addition, we put forward factors necessary to improve the outcomes relating to future studies.

A Non-Damaging Gelled Acid System Based on Surface Modified Nanoparticles

Gelled acid systems based upon gelation of hydrochloric acid (HCl) are used widely in acid stimulation treatments to prevent fluid leak-off into the high permeable zones of a reservoir. The gelled-up fluid system helps retard the acid reaction to allow deeper acid penetration for hydrocarbon productivity enhancement. Conventional in-situ crosslinked gelled acid systems are made up of polyacrylamide gelling agent, iron-based crosslinker, and a breaker chemical in addition to other additives, with the acid as the base fluid. The polymer-based systems can lead to damage to formation due to a variety of reasons including unbroken polymer residue. Additionally, the iron-based crosslinker systems can lead to scaling or precipitation after the acid reacts with the formation, resulting in formation damage and lowering of hydrocarbon productivity. In this paper, we showcase a new nanoparticles-based gelled acid system that does not contain any polymer or iron-based crosslinker that can potentially damage the formation. It comprises nanoparticles, a gelation activator, acidizing treatment additives along with HCl. The new in-situ gelled acid system has low viscosity at surface making it easy to pump. With increase in the temperature and as the acid spends there is a viscosity increase. The viscosification and eventual gelation of the new system can be achieved as the acid reacts with a carbonate formation. As the acid further reacts and continues to spend, the gel demonstrates reduction of viscosity. This assists in a better cleanup post the acidizing treatment. Various experimental techniques were used to highlight the development of the nanoparticle-based acid diversion fluid. The gelation properties of the acid system, as a function of acid strength and temperature, are investigated. Static and dynamic gelation studies as a function of time, temperature and pH are reported. It is demonstrated that the viscosification property is a function of pH and the gelation occurs in a pH widow from 1 to 5 pH units. The gelation performance of the new system is evaluated at temperatures up to 300°F. The effect of different types of surface modification chemistries on the gelation properties is investigated. It is also shown that the gelation and viscosity reduction is entirely a pH dependent phenomenon and does not require any additional breaker chemistry; and therefore provides more control over the system performance. The new gelled acid system overcomes the inherent challenges faced by conventional in-situ crosslinked gelled acid systems; as it is based upon nanoparticles making it less prone to formation damage as compared to a crosslinked polymer-based system.

Produced Water Quality: The Effects of Different Separation Methods for Water and Chemical Floods

Gravity settling represents the main oil-water separation mechanism. Many separation plants rely only on gravity settling with the aid of demulsifiers (direct or reverse breakers) and other chemicals such as water clarifiers if they are required. Yet, other complementary separation methods exist including filtration, flotation, and centrifugation. In terms of results and more specifically with respect to the separated produced-water, the main threshold on its quality is the dispersed oil content. Even with zero discharge and reinjection into hydrocarbon formations, the presence of residual oil in the aqueous phase represents a concern. High oil content results into formation damage and losses in injectivity which necessitates formation stimulations and hence additional operational expenses. In this work, we investigated the effects of different separation techniques on separated water quality. In addition, we studied the impact of enhanced oil recovery (EOR) chemicals on the different separation techniques in terms of efficiency and water quality. Based on the results, we identified potential improvements to the existing separation process. We used synthetic well-characterized emulsions. The emulsions were prepared at the forecast water: oil ratio using dead crude oil and synthetic representative brines with or without the EOR chemicals. To clearly delineate and distinguish the effectiveness of different separation methods, we exacerbated the conditions by preparing very tight emulsions compared with what is observed on site. With that, we investigated three separation techniques: gravity settling, centrifugation, and filtration. First, we used Jar Tests to study gravity settling, then a benchtop centrifuge at two speeds to evaluate centrifugation potential. Finally, for filtration, we tested two options: membrane and deep-bed filtrations. Concerning the water quality, we performed solvent extraction followed by UV analyses to measure the residual oil content as well as light transmission measurements in order to compare the efficiency of different separation methods. The results of analyses suggest that gravity settling was not efficient in removing oil droplets from water. No separation occurred after 20 minutes in every tested condition. However, note that investigated conditions were severe, tighter emulsions are more difficult to separate compared to those currently observed in the actual separation plant. On the other hand, centrifugation significantly improved light transmission through the separated water. Accordingly, we can conclude that the water quality was largely improved by centrifugation even in the presence of EOR chemicals. In terms of filtration, very good water quality was obtained after membrane filtration. However, significant fouling was observed. In the presence of EOR chemicals, filtration lost its effectiveness due to the low interfacial tension with surfactants and water quality became poor. With deep-bed filtration, produced water quality remained good and fouling was no longer observed. However, the benefits from media filtration were annihilated by the presence of EOR chemicals. Based on these results and at least for our case study, we conclude that centrifugation and deep-bed filtration techniques can significantly improve quality of the separated and eventually reinjected water. In terms of the effects of EOR chemicals, the performance of centrifugation is reduced while filtrations are largely impaired by the presence of EOR chemicals. Thereby, integration of any of the two methods in the separation plant will lead to more efficient produced-water reinjection, eliminating formation damage and frequent stimulations. Yet, it is important to note that economics should be further assessed.

Application of a non-ionic bio-surfactant instead of chemical additives for prevention of the permeability impairment of a swelling sandstone oil reservoir

Formation damage is a general term, which refers to any process that reduces the production or injectivity of an oil well. Clay swelling formation damage, due to incompatible fluid invasion, is a common problem in the petroleum industry. In this research, the effect of Acanthophyllum root extract (ACRE), a bio-based surfactant, on the reduction in reservoir permeability impairment has been studied. Some static tests were applied to investigate the chemical interaction between the surfactant and montmorillonite (Mt), including Mt sedimentation test, Free swelling index (FSI) test, Zeta potential tests, particle size measurement, and scanning electron microscopy (SEM). Experiments were followed by coreflood and micromodel tests to verify their effect on preventing permeability reduction and pore plugging in porous media. According to the results, Mt dispersion is unstable in the presence of ACRE solution. ACRE can reduce the FSI from 233.3 (totally hydrated Mt) to 94.3%, representing the reduction in hydration potential. The zeta potential of Mt in ACRE aqueous solution moves toward the lowest magnitude, implying that the water molecules surrounding the Mt particles are unstable. Particle size measurement and SEM analysis proved simultaneously that ACRE solution sustains Mt particles flocculated and prevents delamination. The thermal stability of the ACRE was evaluated by thermogravimetric analysis (TGA), and it showed a suitable resistance to the temperature rise. Eventually, coreflood and micromodel tests revealed that ACRE has a high performance in lowering the permeability impairment and pore plugging. All in all, ACRE showed high potential in preventing Mt swelling and, therefore, formation damage in clay-bearing sandstones.