Commercial Kinetic Hydrate Inhibitor Research Articles

Synthesis and Evaluation of a New Kind of Kinetic Hydrate Inhibitor

A new kind of kinetic hydrate inhibitor (KHI) named KL-1 as the ramification of poly (N-vinyl caprolactam) (PVCap), was synthesized successfully by use of precipitation polymerization. The hydrate inhibition performance of KL-1 was assessed in a high pressure sapphire cell, and the onset time of hydrate formation and maximum subcooling were determined by the visual observation method and compared with the commercial KHIs, including Inhibex 501 and VC-713. Meanwhile, the synergic effect between ethanol and KL-1 developed was also studied in this work. The experimental results show that the onset time of KL-1 measured increases with the increase of the dosage and decrease of subcooling. Compared with the system without kinetic hydrate inhibitor, the morphological behavior of hydrate crystals in the systems containing KL-1 is different, and the hydrate crystals only grow to the gas phase with the hydrate formation. Additionally, based on the measurement of inhibition time, the inhibition performance of KL-1 is superior to Inhibex 501 and VC-713, and shows higher maximum subcooling at the similar conditions. Finally, we also demonstrated that ethanol can be used as synergist to improve the performance of KL-1 remarkably at suitable dosage.

Kinetic Hydrate Inhibitor Studies for Gas Hydrate Systems: A Review of Experimental Equipment and Test Methods

Kinetic hydrate inhibitors (KHIs) have been studied, developed, and used in the oil and gas industries for more than two decades. The main active ingredients in commercial KHI formulations are water-soluble polymers. When dosed at low concentrations (0.1–2.0 wt % active chemical), they are able to retard the gas hydrate formation process and facilitate reliable oil and gas transportation. A considerable amount of research effort on KHI technologies has contributed to an abundance of KHI knowledge, applications, and tailor-made solutions. Whereas previous reviews have concentrated on the chemistry of KHIs, this review article has a particular emphasis on the experimental equipment, hydrate detection tools, and test methods commonly applied in KHI investigations. The underlying mechanisms of KHIs are still not fully understood. The major hypotheses proposed in the literature and supporting experimental and computational evidence are also reviewed.

Performance of Polymer Hydrogels Incorporating Thermodynamic and Kinetic Hydrate Inhibitors

This study investigates the hydrate formation characteristics of hydrogel particles containing thermodynamic or kinetic hydrate inhibitors. Hydrate onset time, hydrate fraction in the liquid phase, and torque changes were determined from the experiments using a high pressure autoclave. To simulate the mixture of water and liquid hydrocarbon encountered in subsea pipelines, decane was added corresponding to an initial 60% water-cut. In the liquid phase a high hydrate fraction was observed in the pure water + decane mixture with a local maximum in torque. For the hydrogel decane mixture, a lower hydrate fraction was observed, and the torque remained stable during the hydrate formation. The addition of 0.5 wt % of a commercial kinetic hydrate inhibitor (Luvicap) to the aqueous phase (with no hydrogel) delayed the hydrate onset time, but several spikes in the torque were observed during the hydrate formation, which suggests that segregation and deposition of hydrate particles is occurring in the liquid phase....

Synthesis and Evaluation of Two New Kinetic Hydrate Inhibitors

Two new kinetic hydrate inhibitors (KHIs) named PVP-B and PVP-BP were synthesized successfully and compared with commercial KHIs such as PVP and Inhibex 55W. PVP-B and PVP-BP are both the ramifications of PVP. They were obtained by introducing a t-butyl group and both t-butyl and phenyl groups into PVP molecules, respectively. The hydrate inhibition performances of KHIs were assessed in a sapphire cell through two kinds of onset times of hydrate formation: TVO, the time when hydrate crystals are initially observed by naked eyes, and TPD, the time when rapid and continuous dropping of system pressure begins. TVO was used to evaluate an KHI’s inhibition performance to hydrate nucleation. The length of time period from TVO to TPD was used to evaluate a KHI’s inhibition performance to hydrate growth. The results demonstrate that both PVP-B and PVP-BP are superior to PVP and Inhibex 55W; PVP-BP has better inhibition performance than PVP-B because of the stronger steric hindrance effects of the phenyl group in ...

Antifreeze proteins as gas hydrate inhibitors

Certain organisms survive low temperatures using a range of physiological changes including the production of antifreeze proteins (AFPs), which have evolved to adsorb to ice crystals. Several of these proteins have been purified and shown to also inhibit the crystallization of clathrate hydrates. They have been found to be effective against structure II (sII) hydrates formed from the liquid tetrahydrofuran, sI and sII gas hydrates formed from single gases, as well as sII natural gas hydrates using a mixture of three gases, as assessed using a variety of instrumentation including stirred reactors, differential scanning calorimetry, nuclear magnetic resonance, Raman spectroscopy, and X-ray powder diffraction. For the most part, AFPs are equal to or more effective than the commercial kinetic hydrate inhibitor (KHI) polyvinylpyrolidone, even under field conditions where saline and liquid hydrocarbons are present. Enclathrated gas analysis has revealed that the adsorption of AFPs to the hydrate surface is distinct from tested commercial KHIs and results in properties that should make these proteins more valuable in some field applications. Efforts to overcome the difficulties of recombinant protein production are ongoing, but in silico models of AFP adsorption to hydrates may offer the opportunity to design commercial KHIs for hydrocarbon recovery and transport with all the attributes of these AFP ”green inhibitors”, including their benefits for human and environmental safety.

N,N-Dimethylhydrazidoacrylamides. Part 2: High-Cloud-Point Kinetic Hydrate Inhibitor Copolymers with N- Vinylcaprolactam and Effect of pH on Performance

Poly(N,N-dimethylhydrazidoacrylamides)s (PDMHAMs) and a series of copolymers of (N,N-dimethylhydrazidoacrylamide) and (N-isopropylacrylamide) were recently investigated as kinetic hydrate inhibitors (KHIs). Poly(N-vinylcaprolactam) (PVCap) and related copolymers have been used as a class of commercial KHIs in the oil and gas industry to prevent plugging of pipelines with gas hydrates. In this study, we have synthesized and investigated the ability of copolymers of DMHAM monomer and VCap monomer to inhibit structure II gas hydrate formation in high-pressure rocking cells at approximately 75 bar. Various polymer molecular weights have been investigated at various pH conditions. It was found that the novel polymers have high cloud points in deionized (DI) water or brine solutions at high or low pH under pressure compared to polyVCap. A 1:2 copolymer of DMHAM/VCap gave the best KHI performance for this class of copolymer with a cloud point at 50 °C in DI water. Also, a 1:1 DMHAM/VCap copolymer gave excellent ...

Structures of Hydrocarbon Hydrates during Formation with and without Inhibitors

The formation of hydrates from a methane-ethane-propane mixture is more complex than with single gases. Using nuclear magnetic resonance (NMR) and high-pressure powder X-ray diffraction (PXRD), we have investigated the structural properties of natural gas hydrates crystallized in the presence of kinetic hydrate inhibitors (KHIs), two commercial inhibitors and two biological ice inhibitors, or antifreeze proteins (AFPs). NMR analyses indicated that hydrate cage occupancy was at near saturation for controls and most inhibitor types. Some exceptions were found in systems containing a new commercial KHI (HIW85281) and a recombinant plant AFP, suggesting that these two inhibitors could impact the kinetics of cavity formation. NMR analysis confirmed that the hydrate composition varies during crystal growth by kinetic effects. Strikingly, the coexistence of both structures I (sI) and II (sII) were observed in NMR spectra and PXRD profiles. It is suggested that sI phases may form more readily from liquid water. Real time PXRD monitoring showed that sI hydrates were less stable than sII crystals, and there was a conversion to the stable phase over time. Both commercial KHIs and AFPs had an impact on hydrate metastability, but transient sI PXRD intensity profiles indicated significantly different modes of interaction with the various inhibitors and the natural gas hydrate system.

THF hydrate crystal growth inhibition with small anionic organic compounds and their synergistic properties with the kinetic hydrate inhibitor poly(N-vinylcaprolactam)

Small, cationic tetraalkylammonium ions (particularly for alkyl=butyl or pentyl) are known to inhibit tetrahydrofuran (THF) and natural gas hydrate crystal growth and have been used as synergists for commercial kinetic hydrate inhibitor polymers (KHIs), such as N-vinylcaprolactam polymers, for a number of years. The ability for small, organic anionic molecules to inhibit (THF) hydrate crystal growth and their potential as KHI synergists in blends with poly(N-vinylcaprolactam) have been investigated. Several series of sodium alkyl carboxylates, sulphates and sulphonates were synthesised. It was found that none of these molecules were capable of inhibiting THF hydrate crystal growth as well as the best tetraalkylammonium salts. Alkyl carboxylates appeared to be more effective as inhibitors than the sulphonates or sulphates. The most effective anionic THF hydrate crystal growth inhibitors had butyl or pentyl groups, with alkyl branching at the tail (i.e. iso- rather than n-isomers) being advantageous. Anionic carboxylate molecules, particularly with isopentyl or isobutyl groups, showed some kinetic inhibition synergy with poly(N-vinylcaprolactam) lowering the onset and catastrophic hydrate formation temperatures in high pressure (78 bar) constant cooling experiments with Structure II hydrates by 1–2 °C when dosed at 2500 ppm compared with using 2500 ppm polymer alone. This synergism was however less than the best tetraalkylammonium salts (alkyl=n-butyl or n-pentyl) at the same test conditions. Sodium butyl sulphonate and sodium 4-methylpentanoate did not prevent hydrate agglomeration with 3.6% brine and decane at 25% water cut in stirred sapphire cells when dosed at 20,000 ppm based on the aqueous phase, whereas 10,000–20,000 ppm active material of several commercially available anti-agglomerants gave fine transportable slurries and no hydrate deposits at the same conditions.

An investigation into the kinetic hydrate inhibitor properties of two imidazolium-based ionic liquids on Structure II gas hydrate

Kinetic hydrate inhibitors (KHIs) are used to prevent gas hydrate formation in gas and oilfield operations. All KHIs discovered to date are water-soluble polymers. However, their performance can be enhanced by certain non-polymeric organic molecules. Recently, it was claimed that certain imidazolium-based ionic liquids could have a dual function, acting as both thermodynamic inhibitors and KHIs (Xiao, C., Adidharma, H., 2009. Chem. Eng. Sci. 64, 1522). As the KHI experimental work was carried out at a temperature of –12 °C, giving a very high subcooling of about 25 °C, we reinvestigated two of these ionic liquids at more typical subsea temperatures and subcoolings. We find that these ionic liquids are very poor KHIs when used alone at 5000–10000 ppm, but they are fairly good synergists for commercial KHIs based on vinyl lactam polymers and hyperbranched poly(ester amide)s. Both ionic liquids showed only weak growth inhibition of tetrahydrofuran hydrate crystals. Finally, both ionic liquids were poorly biodegraded in the OECD306 seawater 28 day biodegradation test.

Kinetic Hydrate Inhibition at Pressures up to 760 Bar in Deep Water Drilling Fluids

Kinetic hydrate inhibitors (KHIs) have been used successfully in the field for about the past 15 years to prevent gas hydrate formation mostly in gas- and oilfield production lines. They work by delaying the nucleation and often also the growth of gas hydrate crystals for periods of time dependent on the subcooling in the system and the absolute pressure. In this paper, we have investigated whether KHIs can be used at very high pressures, particularly for use in ultra-deep-water completion and water-based drilling fluids (WBMs) with high salinity. Compatibility tests were carried out on various brines with several commercial KHIs. Laboratory hydrate equilibrium experiments were conducted on WBMs up to 800 bar. KHI performance tests were carried out in a 500 mL stirred steel autoclave at pressures up to 760 bar. These are much higher pressures than have ever been previously reported for any KHI studies. With the previous knowledge that not only the subcooling but the absolute pressure (70−150 bar) affects ...

Tetrahydrofuran hydrate crystal growth inhibition by hyperbranched poly(ester amide)s

Kinetic hydrate inhibitors (KHIs) are water-soluble polymers designed to delay gas hydrate formation in gas and oilfield operations. Inhibition of growth of gas hydrate crystals is one of the mechanisms by which KHIs have been proposed to act. One class of commercial KHIs is the hyperbranched poly(ester amide)s. We have investigated the ability of a range of structurally different hyperbranched poly(ester amide)s to inhibit the crystal growth of tetrahydrofuran (THF) hydrate which forms a Structure II clathrate hydrate, the most common gas hydrate structure encountered in the upstream oil and gas industry. The results indicate that there is an optimum size of hydrophobic groups attached to the succinyl part of the polymer, which gives best crystal growth inhibition. However, total inhibition was impossible to achieve even at a concentration of 8000 ppm of one of the best polymers at a subcooling of 3.4 °C, tentatively suggesting that polymer adsorption onto natural gas hydrate crystal surfaces is probably not the primary mechanism of kinetic inhibition operating in field applications with this class of KHI.

Class of Kinetic Hydrate Inhibitors with Good Biodegradability

Kinetic hydrate inhibitors have been used successfully in the field for about the last 13 years to prevent gas hydrate formation mostly in gas- and oilfield production lines. They work by delaying the nucleation and often also the growth of gas hydrate crystals for periods of time dependent upon the subcooling in the system. Current commercial kinetic hydrate inhibitors are used for field applications where the subcooling is as high as about 10 °C. In the Norwegian sector of the North Sea, very few of the commercial kinetic hydrate inhibitors are available for use offshore because of poor environmental properties usually related to biodegradability. We have designed and synthesized a class of kinetic hydrate inhibitor, which appears to show good biodegradability (OECD306, >20% in 28 days). Inhibitor performance tests have been carried out in stirred autoclaves (titanium and sapphire) using a natural gas blend and saline water giving structure II hydrates. In the presence of solvents, we have obtained a fa...