Crystal growth inhibition of tetrahydrofuran hydrate with poly(N-vinyl piperidone) and other poly(N-vinyl lactam) homopolymers

Poly(N-vinyl pyrrolidone) (PVP) containing the 5-ring lactam and poly(N-vinyl caprolactam) (PVCap) containing the 7-ring lactam are well-known kinetic hydrate inhibitors (KHIs). For the first time we have synthesised and studied the performance of poly(N-vinyl piperidone) (PVPip), containing the 6-ring lactam, as a kinetic hydrate inhibitor. In the first part of the study we have investigated the ability of PVPip to inhibit the growth of tetrahydrofuran SII hydrate crystals. The results are compared to those of PVP and PVCap. Various polymer molecular weights have been investigated at varying subcoolings. PVPip shows an intermediate growth inhibition performance compared to PVP and PVCap at similar polymer molecular weights. In addition, the weight percentage concentration of polymer needed to achieve complete THF hydrate crystal growth inhibition increases as the polymer molecular weight decreases.     

酸功能化离子液体催化合成仲丁醇的反应动力学(英文)

The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4 as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a ho-mogeneous kinetic model was established. The results show that the reaction heatΔH is 10.94 × 103 J·mol?1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea?are 60.38 × 103 and 49.44 × 103 J·mol?1, respectively.     

Studies on some zwitterionic surfactant gas hydrate anti-agglomerants

Low dosage hydrate inhibitors (LDHIs) are a recently developed hydrate control technology, which can be more cost-effective than traditional practices such as the use of thermodynamic inhibitors e.g. methanol and glycols. Two classes of LDHI called kinetic inhibitors (KHIs) and anti-agglomerants (AAs) are already being successfully used in the field. This paper describes efforts to develop new classes of AAs based on zwitterionic surfactants. The chemistry of the new surfactants is described along with experiments to determine their performance carried out in high pressure cells and a wheel loop. The results indicate positive performance for some products but not as good as a commercial quaternary ammonium-based surfactant AA. It was also shown that best results were obtained if the two ionic groups are spaced far apart from each other in the molecule. The best AA molecule tested was 3-[N,N- dibutyl-N-(2-(3-carboxy-pentadecenoyloxy)propyl)]ammonio propanoate. It performed well in sapphire cell tests at up to 15.9 °C subcooling. Its performance was fairly good in the wheel loop at 13.4 °C subcooling, but failed at 16.5 °C subcooling. 3-[N,N-dibutyl-N-(2- hydroxypropyl)ammonio]propanoate was also shown to be an excellent synergist for polyvinylcaprolactam KHIs.     

Determining gas hydrate kinetic inhibitor effectiveness using emulsions

In this study we measure the effect of hydrate kinetic inhibition in emulsions. Because hydrate nucleation is stochastic, many experiments normally are needed to obtain accurate analysis of the effectiveness of kinetic inhibitors. Using differential scanning calorimetry (DSC), we show how emulsions can reduce the number of kinetic samples needed to obtain a statistical analysis of the effectiveness of polyvinylcaprolactam, PVCap, a common kinetic inhibitor. PVCap is shown to delay the average hydrate nucleation time and also causes hydrate nucleation to become more stochastic. This novel method uses less material and experimental time compared to traditional methods used to test kinetic inhibitors.     

Unusual kinetic inhibitor effects on gas hydrate formation

Gas hydrate formation experiments were conducted with a methane-ethane mixture at 273.7 or 273.9 K and 5100 kPa and using water droplets or water contained in cylindrical glass columns. The effect of kinetic inhibitors and the water/solid interface on the induction time for hydrate crystallization and on the hydrate growth and decomposition characteristics was studied. It was found that inhibitors GHI 101 and Luvicap EG delayed the onset of hydrate nucleation. While this inhibition effects has been reported previously some unusual behaviour was observed and reported for the first time. In particular, the water droplet containing GHI 101 or Luvicap EG was found to collapse prior to nucleation and spread out on the Teflon surface. Subsequently, hydrate was formed as a layer on the surface. Catastrophic growth and spreading of the hydrate crystals was also observed during hydrate formation in the glass columns in the presence of the kinetic inhibitor. Finally, when polyethylene oxide (PEO) was added into the kinetic inhibitor solution the memory effect on the induction time decreased dramatically.     

天然气水合物及其抑制剂的研究和应用

在简述天然气水合物结构和性质的基础上,介绍了天然气水合物热力学抑制剂、动力学抑制剂、防聚剂等的研究现状、作用机理、种类、应用范围以及存在的缺陷。     

Studies on some alkylamide surfactant gas hydrate anti-agglomerants

Low dosage hydrate inhibitors (LDHIs) are a recently developed hydrate control technology, which can be more cost-effective than traditional practices such as the use of thermodynamic inhibitors e.g., methanol and glycols. Two classes of LDHI called kinetic inhibitors (KHIs) and anti-agglomerants (AAs) are already being successfully used in the field. This paper describes efforts to develop new classes of AA surfactant with one or two alkylamide groups in the polar head. The goal was to find an AA that was as good as commercial quaternary AAs, which would be economically competitive and more environmentally friendly. The chemistry and environmental properties of the new surfactants are described along with experiments to determine their performance carried out in high-pressure sapphire cells and a wheel loop. The results indicate positive performance for some products but not as good as a commercial quaternary ammonium-based surfactant AA. The best surfactants had one or two carbonylpyrrolidine or isopropylamide groups in the head. The performance of the best AAs was found to be dependent on the hydrocarbon phase and salinity of the water phase.     

An investigation on gas hydrate formation and slurry viscosity in the presence of wax crystals

Clarifying the interaction effect between hydrate and wax is of great significance to guarantee operation safety in deep water petroleum fields. Experiments in a high‐pressure hydrate slurry rheological measurement system were carried out to investigate hydrate formation and slurry viscosity in the presence of wax crystals. Results indicate that the presence of wax crystals can prolong hydrate nucleation induction time, and its influence on hydrate growth depends on multiple factors. Higher stirring rate can obviously promote hydrate growth rate, while its influence on hydrate nucleation induction time is complicated. Higher initial pressure will promote hydrate formation. Gas hydrate slurry shows a shear‐thinning behavior, and slurry viscosity increases with the increase of wax content and initial pressure. A semiempirical viscosity model showing a well‐fitting is established for hydrate slurry with wax crystals by considering the aggregation and breakage of hydrate particles, wax crystals, and water droplets. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3502–3518, 2018     

Enhancement of the performance of gas hydrate kinetic inhibitors with polyethylene oxide

Inclusion of polyethylene oxide into a kinetic inhibitor solution was found to enhance the performance of the inhibitor. Polyethylene oxide is a commercially available high molecular weight polymer that is not a kinetic inhibitor by itself. The hydrate formation experiments in the presence of the various inhibitor solutions were conducted in a vessel in a semi-batch manner at constant pressure and using methane and methane-ethane gas mixtures. In some experiments a non-aqueous liquid phase (n-heptane) was also present. The induction time, the gas uptake and the temperature were measured. It was found that the induction time is prolonged in the presence of the additive by an order of magnitude in some cases compared to the inhibitor only.     

Characterization of gas hydrates with PXRD, DSC, NMR, and Raman spectroscopy

Structure I (sI) and H (sH) hydrates containing methane were synthesized and characterized with PXRD, DSC, NMR, and Raman spectroscopy. Three well-known large molecule guest substances (LMGSs) were selected as sH hydrate formers: 2,2-dimetylbutane (NH), methylcyclohexane (MCH), and tert-butyl methyl ether (TBME). The solid phase analysis confirmed the presence of sH hydrate whenever a LMGS was present. The presence of a non-hydrate former (n-heptane) did not affect the methane hydrate structure or cage occupancies. Ice to hydrate conversion was limited when the LMGS amount was less than stoichiometric and synthesized at low methane pressure, but nearly complete conversion was achieved with temperature ramping and excess LMGS. The methane occupancies were found to depend on the type of LMGS and increased with pressure. The hydrate with TBME was found to have the smallest methane content followed by the hydrates with NH and MCH. Both NMR and Raman identified methane and LMGS signals from the hydrate phase, however, the cage occupancy values of sH hydrate can only be obtained from NMR spectroscopy. The hydrate structures, ice to hydrate conversion, gas content in hydrate and cage occupancy from the various measurements are consistent with each other.     

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.     

近冰点多孔介质中甲烷水合物生成的温度敏感性

水合物技术是实现天然气储存、气体分离、海水淡化和二氧化碳捕集等的潜在可行途径之一,水合物技术为了降低生产成本同时又保持系统流动性,通常选择冰粉或冰浆等形式使生成反应在冰点附近进行;自然界的天然气水合物多数赋存于天然的多孔介质内,随着全球气温升高,甲烷水合物在临界条件附近的敏感性会导致储层的稳定性下降及潜在的甲烷大量释放,尤其是受气候变化影响较大的冻土带天然气水合物,其储层温度一般也处于冰点附近。本工作研究了硅砂(0.1~0.5 mm)中甲烷水合物在近冰点的形成过程与动力学特征,分别在273.75, 273.85和273.95 K小温差下研究了压力、温度、反应速率和甲烷吸收量变化,分析并计算了硅砂孔隙中水合物、水相和气相的最终体积饱和度。温度与反应速率的变化表明,水合物生成过程呈现出明显的三个阶段,在不同的阶段,温度和反应速率表现出独特的变化特征如峰值、持续时间等,同时对环境温度的敏感性非常强,温度升高后甲烷水合物生长速率及其在孔隙中的饱和度均有所降低,低温下水合物生长点晚及对应诱导期持续更长。     

Is subcooling the right driving force for testing low-dosage hydrate inhibitors?

The degree of subcooling is usually used as the driving force for hydrate formation; however, it does not encompass the effect of pressure. A comprehensive driving force for hydrate formation is a function of pressure, temperature, and gas composition; however, its calculation is not as simple as that of subcooling. In this work, by application of the two latest driving force expressions for hydrate formation, the relationships between subcooling and the true driving force at different conditions for pure gas-water and natural gas-water systems are analysed. The effect of pressure on the induction time in the presence and absence of a kinetic inhibitor have been tested at similar degrees of subcooling.The results show that for pure gas-water systems subcooling is proportional to the driving force, with a good approximation over a wide pressure range at isothermal conditions. However, for multicomponent systems (e.g., natural gases), the driving force is more than that suggested by subcooling at some pressures. Changes of driving force with pressure at a constant degree of subcooling for the above systems have been presented. The results show that the pressure has no significant effect on the driving force (at a constant degree of subcooling) above a certain pressure range. The experimental results show that in a natural gas-water system at constant degree of subcooling the induction time is not significantly affected by pressure. However, in the presence of the kinetic inhibitor tested in this study, high-pressure conditions decreased the induction time.