Search Results (39)

During the transportation of oil and gas pipelines, the adhesion and aggregation of hydrate particles on the pipe wall are prone to cause pipeline blockage, which seriously impairs the safe and efficient transportation of energy. Taking cyclopentane hydrates as the research object, this study investigated the effects of contact time, wall wettability, and the concentration of kinetic hydrate inhibitor poly(N-vinylcaprolactam) (PVCap) on the adhesion force between hydrates and the wall of X80 pipeline steel by combining a high-precision micromechanical force measurement system with microscopic morphology observation and analysis. The results show that the adhesion force increases with prolonged contact time: it is dominated by capillary liquid bridge force in the initial contact stage with slow growth, and after exceeding the critical time, the sintering effect becomes the dominant factor, leading to a rapid rise in adhesion force that eventually tends to stabilize. Wall wettability significantly influences the adhesion force, and enhanced wettability improves the adhesion force by increasing the liquid bridge volume and the hydrate–wall contact area. PVCap concentration exerts a non-monotonic effect on adhesion force—first decreasing and then increasing. At low concentrations (0.25–1 wt%), PVCap molecules adsorb on the hydrate surface to form a physical barrier, reducing adhesion force. At high concentrations (1.5–2 wt%), excessive PVCap damages hydrate shell integrity, releasing free water to expand the liquid bridge volume and increase adhesion force. This study provides a theoretical basis for eliminating or reducing hydrate blockage in deep-sea oil and gas pipelines. Full article

Readily degradable low-dose hydrate inhibitors are of great significance for flow assurance in the petroleum industry. Recently, α-lipoic acid (LA) was shown to undergo ring-opening reaction via reversible addition–fragmentation chain-transfer copolymerization with acrylamides to introduce labile disulfide bonds into the stable vinyl polymer backbone. Here, LA was copolymerized with acryloyl morpholine (AM) to evaluate their performance as kinetic hydrate inhibitors. Degradability was confirmed for the copolymers with 20 mol.% LA (AM/LA20, M_n = 19 → 9 kDa) after disulfide reduction. Thermogravimetric analysis also indicated faster thermal degradation of AM/LA due to the incorporation of weaker S-S and S-C linkages. Increasing LA content reduced hydrophilicity, and the copolymers were treated with NaOH to ensure water solubility. However, at 700 ppm, poly(AM) homopolymer reduced methane consumption during hydrate growth to 54% with respect to the uninhibited system, while gas consumption for the carboxylate AM/LA20 reached 78%. An advantageous feature of LA is its carboxylic acid, allowing desired functionalities to be grafted onto the degradable copolymer. Isopropyl amine (IPAm) was coupled with LA to form an amide known to be effective during hydrate inhibition (LA(IPAm)). The copolymer AM/LA(IPAm)20 demonstrated better water solubility compared to the original AM/LA20. Furthermore, the desirable IPAm functionality allowed the hydrate inhibition to be re-established at 54%, nearly recovering the performance of the poly(AM) homopolymer. This article assesses the application of LA and LA derivatives as building blocks for degradable amide-based kinetic hydrate inhibitors by validating their degradability with material characterizations and their inhibition performance during structure I hydrate growth. Full article

During deepwater drilling operations, when influx gas invades the wellbore, gas hydrates may form through the combination of the gas with free water in the drilling fluid under favorable temperature and pressure conditions. This process can alter the physical properties and flow behavior of the wellbore fluid, potentially leading to safety incidents. To prevent natural gas hydrate formation, mitigate wellbore blockages caused by hydrates, and address the associated safety hazards, this study conducted laboratory experiments to investigate hydrate formation and remediation under multiple deepwater drilling conditions. The hydrate formation boundaries for four different drilling fluid systems—seawater-based bentonite mud, seawater polymer mud, Plus/KCl mud, and HEM mud—were determined for varying well depths and pressure–temperature conditions, and corresponding trend lines were fitted. Key results reveal that a higher carbon content promotes hydrate formation, and the phase equilibrium curves also reveal significant differences among the four drilling fluids. The hydrate aggregation states and blockage processes were clarified for three typical drilling scenarios: drilling, well killing, and drilling suspension. Hydrate formation risk is negligible during normal circulation but increases dramatically during well-killing operations, significantly shrinking the safe operational window. A comparative analysis identified that adding 1% P(M-VCL), a kinetic hydrate inhibitor, to the drilling fluid was the most effective solution, demonstrating superior performance in delaying hydrate nucleation and preventing agglomeration. The study established a complete formation–inhibition–remediation approach for hydrate management in deepwater drilling, thereby enhancing operational safety and efficiency. Full article

The safe exploitation of marine natural gas hydrates, a promising cleaner energy resource, is hindered by reservoir instability during drilling. The inherent temperature–pressure sensitivity and cementation of hydrate-bearing sediments leads to severe operational risks, including borehole collapse, gas invasion, and even blowouts. This review synthesizes the complex instability mechanisms and evaluates the state of the art in inhibitive, wellbore-stabilizing drilling fluids. The analysis first deconstructs the multiphysics-coupled failure process, where drilling-induced disturbances trigger a cascade of thermodynamic decomposition, kinetic-driven gas release, and geomechanical strength degradation. Subsequently, current drilling fluid strategies are critically assessed. This includes evaluating the limitations of conventional thermodynamic inhibitors (salts, alcohols, and amines) and the advancing role of kinetic inhibitors and anti-agglomerants. Innovations in wellbore reinforcement using nanomaterials and functional polymers to counteract mechanical failure are also highlighted. Finally, a forward-looking perspective is proposed, emphasizing the need for multiscale predictive models that bridge molecular interactions with macroscopic behavior. Future research should prioritize the development of “smart”, multifunctional, and green drilling fluid materials, integrated with real-time monitoring and control systems. This integrated approach is essential for unlocking the potential of marine gas hydrates safely and efficiently. Full article

With the continuous growth of global energy demand and the gradual depletion of traditional fossil energy reserves, natural gas hydrates have attracted widespread attention as a potential clean energy source due to their vast reserves and wide distribution. Although various extraction methods, including depressurization, thermal stimulation, chemical inhibitors, and displacement methods, have been proposed, there are still challenges, such as low extraction efficiency, poor sustainability, and high costs, making it difficult to achieve large-scale engineering applications. Among these, the use of gases such as CO₂ for displacement extraction of natural gas hydrates can both develop hydrate resources and sequester CO₂, achieving a win–win situation for resource development and greenhouse gas reduction. This paper provides a detailed review of the multi-gas displacement extraction technology for natural gas hydrates, systematically summarizes the latest progress in thermodynamic and kinetic studies, analyzes the technical advantages and feasibility of combining displacement methods with traditional techniques, and explores the effects of multi-gas mixtures, such as N₂, CO₂, and H₂, and their ratios on hydrate extraction efficiency. Finally, this paper summarizes the technical challenges faced by displacement extraction methods for hydrates and offers future research directions to promote the development of multi-gas displacement technology for natural gas hydrates. Full article

The hydrate blockage avoidance performance of two anti-agglomerants (coconut amidopropyl dimethylamine, propylene bis (octadecylamidopropyl dimethylammonium chloride)) and their mixtures with polyvinylpyrrolidone (PVP) was tested in a high-pressure rocking cell apparatus. The effect of gas–liquid ratio, water content and PVP concentration were analyzed. A method for evaluating the kinetic inhibiting and anti-agglomerating performance of hydrate inhibitors was established. It was found that coconut amidopropyl dimethylamine had good anti-agglomerating performance at a low gas–liquid ratio (0.5) and various water content levels (20~80%), while propylene bis (octadecylamidopropyl dimethylammonium chloride) had a good anti-agglomerating performance only at a low gas–liquid ratio (0.5) and high water content (80%), and the hydrate volume fraction was up to 23.27% for good anti-agglomeration. When PVP was mixed with the above two anti-agglomerants, it was found that coconut amidopropyl dimethylamine could significantly reduce the kinetic inhibition performance of PVP, while propylene bis (octadecylamidopropyl dimethylammonium chloride) had no significant effect on the kinetic inhibition performance of PVP. The maximum subcooling was 4.4 °C. PVP had no significant effect on the anti-agglomerating performance of the two anti-agglomerants, and the maximum hydrate volume fraction was 18.87% when the agglomeration was well inhibited. Full article

Gas hydrate inhibition using chemicals has been under continuous investigation, and several modelling studies have been published since its inception. Since it is not always feasible to conduct experimental research, it is especially crucial to forecast the conditions under which gas hydrates may form and dissociate in the presence of chemical inhibitors. As a result, a reliable forecasting tool is vital. This article provides an exhaustive review of various modelling methodologies in the context of gas hydrate chemical inhibition. The key aspects of empirical models, thermodynamic models, kinetic models, artificial intelligence-based models and quantum chemistry-based models are presented. Critical analysis of each modelling approach has been performed, highlighting strengths, limitations, and areas where further investigations are still crucial. Rapid progress has been made with respect to gas hydrate modelling approaches in the context of chemical inhibition; however, further research is still vital to bridge the gaps that have been identified in this review. Potential improvements to existing models have been proposed, particularly in terms of integrating experimental data and utilizing hybrid approaches, which could serve as valuable future directions for the field. Full article

As the understanding of natural gas hydrates as a vast potential resource deepens, their importance as a future clean energy source becomes increasingly evident. However, natural gas hydrates trend towards secondary generation during extraction and transportation, leading to safety issues such as pipeline blockages. Consequently, developing new and efficient natural gas hydrate inhibitors has become a focal point in hydrate research. Kinetic hydrate inhibitors (KHIs) offer an effective solution by disrupting the nucleation and growth processes of hydrates without altering their thermodynamic equilibrium conditions. This paper systematically reviews the latest research progress and development trends in KHIs for natural gas hydrates, covering their development history, classification, and inhibition mechanisms. It particularly focuses on the chemical properties, inhibition effects, and mechanisms of polymer inhibitors such as polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap). Studies indicate that these polymer inhibitors provide an economical and efficient solution due to their low dosage and environmental friendliness. Additionally, this paper explores the environmental impact and biodegradability of these inhibitors, offering guidance for future research, including the development, optimization, and environmental assessment of new inhibitors. Through a comprehensive analysis of existing research, this work aims to provide a theoretical foundation and technical reference for the commercial development of natural gas hydrates, promoting their safe and efficient use as a clean energy resource. Full article

Polyetheramine (PEA) is a swelling inhibitor used to address engineering challenges arising from the interaction between montmorillonite (Mt) and water. This study comprehensively investigates the adsorption characteristics of PEA on three representative expansive clay samples: Na-Mt, Ca-Mt, and engineered expansive soil. Additionally, the desorption of exchangeable ions is examined. The findings reveal that a two-stage adsorption kinetic model and a pseudo-second-order kinetic model can properly describe the adsorption kinetics of PEA on expansive clays. PEA exhibits a strong capacity for ion exchange with sodium ions, while the exchange capacity for calcium ions is limited. Both protonated and non-protonated PEA contribute to rapid adsorption processes. The adsorption isotherms are well-fitted by the Langmuir and Freundlich models, with the Langmuir model being reasonable. At lower equilibrium concentrations, a higher proportion of the adsorption amount is attributed to ion exchange compared to higher equilibrium concentrations. Ion exchange emerges as the primary factor contributing to the adsorption of PEA on Na-Mt, whereas the adsorption of PEA on Ca-Mt and expansive soil is primarily attributed to physical adsorption by non-protonated PEA. X-ray diffraction results reveal significant intercalation effects of PEA as they penetrate the interlayer space and hinder interlayer ion hydration. Fourier transform infrared spectrum results demonstrate that the adsorption of PEA minimally impacts the framework of Mt structural units but primarily reduces the adsorbed water content. Clay-PEA composites exhibit a decreased affinity for water. Zeta potential experiments indicate that the adsorption of PEA significantly diminishes the surface potential of clay-PEA composite particles, effectively inhibiting their hydration dispersion. Full article

The development of a lipid nano-delivery system was attempted for three specific poly (ADP-ribose) polymerase 1 (PARP1) inhibitors: Veliparib, Rucaparib, and Niraparib. Simple lipid and dual lipid formulations with 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1′-glycerol) sodium salt (DPPG) and 1,2-dipalmitoyl-sn-glycero-3-phosphocoline (DPPC) were developed and tested following the thin-film method. DPPG-encapsulating inhibitors presented the best fit in terms of encapsulation efficiency (>40%, translates into concentrations as high as 100 µM), zeta potential values (below −30 mV), and population distribution (single population profile). The particle size of the main population of interest was ~130 nm in diameter. Kinetic release studies showed that DPPG-encapsulating PARP1 inhibitors present slower drug release rates than liposome control samples, and complex drug release mechanisms were identified. DPPG + Veliparib/Niraparib presented a combination of diffusion-controlled and non-Fickian diffusion, while anomalous and super case II transport was verified for DPPG + Rucaparib. Spectroscopic analysis revealed that PARP1 inhibitors interact with the DPPG lipid membrane, promoting membrane water displacement from hydration centers. A preferential membrane interaction with lipid carbonyl groups was observed through hydrogen bonding, where the inhibitors’ protonated amine groups may be the major players in the PARP1 inhibitor encapsulation mode. Full article

This study aims to address the environmental impact of using common commercial hydrate inhibitors such as Methanol (MeOH) in extremely cold oil and gas environments. As a greener alternative, Pectic Polysaccharides (pectin) can act as a kinetic hydrate inhibitor (KHI) to delay hydrate formation. We evaluated the performance of amidated pectin (AMP), a type of pectin with higher electronegative functional groups, using a high-pressure micro-differential scanning calorimeter (HP µ-DSC) under isobaric conditions with constant cooling. We compared AMP to low-methoxylated pectin (LMP) and high-methoxylated pectin (HMP) and found that AMP was the best KHI among the tested pectin types. At a concentration of 1.0 wt.%, the AMP Relative Inhibitor Performance (RIP) was 0.10, and at 0.1 wt.%, it had an RIP of 0.07, which were the only positive RIPs obtained amongst the tested KHIs. The results suggest that AMP can be a sustainable KHI option in extremely cold environments where the KHI effectiveness typically declines. Full article

This review covers the types and applications of chemical inhibitors of gas hydrate formation in the oil and gas industry. The main directions of the development of new types of highly effective and environmentally safe “green” kinetic hydrate inhibitors (KHIs) based on biopolymers are analyzed. The structure, physicochemical properties, efficiency of gas hydrate formation inhibition, and commercial prospects of polysaccharides in preventing and controlling the formation of gas hydrates are considered. The criteria for their selection, current experimental data, and the mechanism of inhibition are presented. Recent research in the development of cost-effective, efficient, and biodegradable KHIs for industrial applications in the oil and gas industry is also presented. Full article

Polyvinylcaprolactam (PVCap) is an economic kinetic inhibitor for hydrate formation in pipelines during oil and gas transportation. However, its application is limited because of the low inhibition performance under certain conditions. In this work, a modified PVCap on its chain end is proposed. 2-amino-3-propionic acid mercapto-terminated polyvinyl caprolactam (PVCap-NH${}_2$-COOH) was synthesized and its performance as a KHI for methane hydrate formation was evaluated under different conditions. Results showed that the performance of PVCap-NH${}_2$-COOH as a KHI was better than that of PVCap at the same concentrations. Gas hydrate samples with 1 wt.% PVCap-NH${}_2$-COOH were measured using Raman spectroscopy, XRD, and cryo-SEM. PVCap-NH${}_2$-COOH had a selective action on a specific crystal surface of the hydrates and could prevent methane molecules from entering large cages. Its inhibition ability increased with the decrease in the occupancy rate of large cages. The morphology of the gas hydrate crystal changed from porous in a pure water system to a chaotic but compact structure state in the system with PVCap-NH${}_2$-COOH. Full article

The widespread use of nanomaterials in vaccines, therapeutics, and industrial applications creates an increasing demand for understanding their ingestion by living cells. Researchers in the field have called for a more robust understanding of physical/chemical particle–cell interactions and a means to determine the particles ingested per cell. Using superparamagnetic nanobeads, we measured the beads per cell and quantified the kinetics of the receptor-independent endocytosis of particles having seven surface chemistries. Poly(ethylene glycol) (PEG)-coated nanoparticles were ingested less effectively by cultured Chinese hamster ovary (CHO-K1) cells and more effectively by aminated nanoparticles than starch-coated particles. The cells ingested 2 to 4 × 10⁵ of the most attractive particles. The interplay between Van der Waals and coulombic potentials was quantified on the basis of Derjaguin–Landau–Verwey–Overbeek (DLVO) theory modified to include hydration repulsion using physical parameters of the seven surface chemistries. Using dose–response curves for inhibitors of clathrin- or caveolae-dependent ingestion, we quantified how particle surface chemistry determines which endocytic pathway is used by the cell. Such characterization can be useful in predicting nanomaterial uptake in medical and toxicological applications and in the selection of particle surface chemistries for receptor-dependent endocytosis. Full article

Gas hydrate blockage is a major issue that the production and transportation processes in the oil/gas industry faces. The formation of gas hydrates in pipelines results in significant financial losses and serious safety risks. To tackle the flow assurance issues caused by gas hydrate formation in the pipelines, some physical methods and chemical inhibitors are applied by the oil/gas industry. The physical techniques involve subjecting the gas hydrates to thermal heating and depressurization. The alternative method, on the other hand, relies on injecting chemical inhibitors into the pipelines, which affects gas hydrate formation. Chemical inhibitors are classified into high dosage hydrate inhibitors (thermodynamic hydrate inhibitors (THI)) and low dosage hydrate inhibitors (kinetic hydrate inhibitors (KHI) and anti-agglomerates (AAs)). Each chemical inhibitor affects the gas hydrate from a different perspective. The use of physical techniques (thermal heating and depressurization) to inhibit hydrate formation is studied briefly in this review paper. Furthermore, the application of various THIs (alcohols and electrolytes), KHIs (polymeric compounds), and dual function hydrate inhibitors (amino acids, ionic liquids, and nanoparticles) are discussed thoroughly in this study. This review paper aims to provide a complete and comprehensive outlook on the fundamental principles of gas hydrates, and the recent mitigation techniques used by the oil/gas industry to tackle the gas hydrate formation issue. It hopes to provide the chemical engineering platform with ultimate and effective techniques for gas hydrate inhibition. Full article