Kinetic studies of gas hydrate formation with low-dosage hydrate inhibitors

Pipeline blockage by gas hydrates is a serious problem in the petroleum industry. Low-dosage inhibitors have been developed for its cost-effective and environmentally acceptable characteristics. In a 1.072-L reactor with methane, ethane and propane gas mixture under the pressure of about 8.5 MPa at 4 °C, hydrate formation was investigated with low-dosage hydrate inhibitors PVP and GHI1, the change of the compressibility factor and gas composition in the gas phase was analyzed, the gas contents in hydrates were compared with PVP and GHI1 added, and the inhibition mechanism of GHI1 was discussed. The results show that PVP and GHI1 could effectively inhibit the growth of gas hydrates but not nucleation. Under the experimental condition with PVP added, methane and ethane occupied the small cavities of the hydrate crystal unit and the ability of ethane entering into hydrate cavities was weaker than that of methane. GHI1 could effectively inhibit molecules which could more readily form hydrates. The ether and hydroxy group of diethylene glycol monobutyl ether have the responsibility for stronger inhibition ability of GHI1 than PVP.     

Fleroxacin hydrochloride hydrate

In the structure of the title compound, 4‐[3‐carboxy‐6,8‐di­fluoro‐1‐(2‐fluoro­ethyl)‐1,4‐di­hydro‐4‐oxo‐7‐quinolyl]‐1‐methyl­piperazinium chloride hydrate, C₁₇H₁₉F₃N₃O₃⁺·­Cl^?·­H₂O, the quinoline and its substituents, except for the fluoro­ethyl group, are coplanar, while the piperazinium moiety exists in a chair form. There are π–π‐stacking interactions between the quinoline rings, and intra‐ and intermolecular hydrogen bonds in the crystal.     

Search for memory effects in methane hydrate: structure of water before hydrate formation and after hydrate decomposition

Neutron diffraction with HD isotope substitution has been used to study the formation and decomposition of the methane clathrate hydrate. Using this atomistic technique coupled with simultaneous gas consumption measurements, we have successfully tracked the formation of the sI methane hydrate from a water/gas mixture and then the subsequent decomposition of the hydrate from initiation to completion. These studies demonstrate that the application of neutron diffraction with simultaneous gas consumption measurements provides a powerful method for studying the clathrate hydrate crystal growth and decomposition. We have also used neutron diffraction to examine the water structure before the hydrate growth and after the hydrate decomposition. From the neutron-scattering curves and the empirical potential structure refinement analysis of the data, we find that there is no significant difference between the structure of water before the hydrate formation and the structure of water after the hydrate decomposition. Nor is there any significant change to the methane hydration shell. These results are discussed in the context of widely held views on the existence of memory effects after the hydrate decomposition.     

含低剂量抑制剂体系气体水合物生成动力学

水合物管道堵塞是油气工业安全生产的重要问题之一, 目前低剂量抑制剂以其经济性、环境友好性等优点, 逐步取代传统抑制剂. 文中在8.5 MPa、4 ℃条件下, 1.072 L反应釜内, 采用甲烷、乙烷和丙烷混和气, 研究了含低剂量抑制剂聚乙烯吡咯烷酮(PVP)和GHI1的水合物生成体系反应过程, 计算分析了压缩因子和自由气量随反应时间的变化, 对比了在相同反应程度下添加PVP和GHI1后水合物含气量的区别, 探讨了GHI1组合抑制剂的抑制机理. 实验结果表明PVP和GHI1能抑制水合物生长, 不能有效抑制水合物成核; 添加PVP的体系, 在实验气体组成下, 甲烷乙烷进入水合物小晶穴, 并且甲烷优先进入小晶穴; GHI1对丙烷乙烷的抑制能力强于甲烷; 对比GHI1和PVP的反应过程, 认为协同剂二乙二醇丁醚的羟基和醚类结构加强反应体系中的氢键, 和PVP结合使用, 通过氢键和空阻达到抑制效果.     

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

The composition of methane hydrate, namely n(w) for CH4.n(w)H2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but n(w) may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n(w) = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4.5.99(+/-0.07)H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence.     

Dealkylation with hydrazine hydrate

Cleavage of one alkyl group occurs in the reaction of 4-amino-3,5-di(alkylthio)-1,2,4-triazoles with hydrazine hydrate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1708–1710, December, 1973.     

High-pressure clathrate hydrate of acetone

X-ray diffraction study of quenched sample of acetone clathrate hydrate synthesized at 0.8 GPa was carried out. It was shown that the host frameworks of the hydrate comprise uniform cavities which are similar to that of recently characterized structure of high-pressure tetrahydrofurane hydrate. The unique peculiarity of investigated hydrate is decrease in the crystallographic symmetry of the hydrate arising from ordering in guest subsystem.     

Alaninyl­tryptophan hydrate,glycyl­tryptophan dihydrate and tryptophyl­glycine hydrate

The crystal structures of the title tryptophan‐containing dipeptides, C₁₄H₁₇N₃O₃·H₂O, (I), C₁₃H₁₅N₃O₃·2H₂O, (II), and C₁₃H₁₅N₃O₃·H₂O, (III), respectively, contain at least one water mol­ecule of solvation. As a result, the crystal packing of these compounds is composed of regions of water‐mediated hydrogen bonding and tryptophan ring‐to‐ring stacking separated by the length of the mol­ecule. The tryptophan rings stack in a continuous layer that, when viewed edge‐on from the outermost part of the tryptophan ring, exhibits a herring‐bone motif. However, owing to the lack of direct overlap of adjacent rings, no degree of π contact or long‐range delocalization of ring systems is possible here. The overall molecular conformations of (I) and (III) contain a folding of one peptide over the other, such that a minimum in molecular volume occurs without any intramolecular hydrogen bonding. In these two dipeptides, extensive hydrogen bonding is observed to and from the single water mol­ecule of solvation. In the crystal structure of (II), however, an extended mol­ecule conformation complements a more extensive hydrogen‐bonding scheme involving two water mol­ecules of solvation per dipeptide.     

Quasiamorphous state of methane hydrate

It is established experimentally that at temperatures above 0°C formation of methane hydrate starts with the appearance of thin films of this substance on the surface of water; during isothermal storage, the films permeate throughout the whole volume of the sample. The maximal content of methane hydrate is several (volume) per cent. The viscosity of the sample is much lower than that of ice and much higher than that of water. A. A. Galkin Donetsk Physicotechnical Institute, Ukrainian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 86–91, January–February, 1998.     

Kinetic inhibitor of hydrate crystallization

We present the results of a combined theoretical/experimental study into a new class of kinetic inhibitor of gas hydrate formation. The inhibitors are based on quaternary ammonium zwitterions, and were identified from a computational screen. Molecular dynamics simulations were used to characterize the effect of the inhibitor on the interface between a type II hydrate and natural gas. These simulations show that the inhibitor is bifunctional, with the hydrophobic end being compatible with the water structure present at the hydrate interface, while the negatively charged functional group promotes a long ranged water structure that is inconsistent with the hydrate phase; the sulfonate-induced structure was found to propagate strongly over several solvation shells. The compound was subsequently synthesized and used in an experimental study of both THF and ethane hydrate formation, and was shown to have an activity that was comparable with an existing commercial kinetic inhibitor: PVP.     

Alcohol cosurfactants in hydrate antiagglomeration

Because of availability, as well as economical and environmental considerations, natural gas is projected to be the premium fuel of the 21st century. Natural gas production involves risk of the shut down of onshore and offshore operations because of blockage from hydrates formed from coproduced water and hydrate-forming species in natural gas. Industry practice has been usage of thermodynamic inhibitors such as alcohols often in significant amounts, which have undesirable environmental and safety impacts. Thermodynamic inhibitors affect bulk-phase properties and inhibit hydrate formation. An alternative is changing surface properties through usage of polymers and surfactants, effective at 0.5 to 3 weight % of coproduced water. One group of low dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are antiagglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, work on hydrate antiagglomeration is very limited. This work centers on the effect of small amounts of alcohol cosurfactant in mixtures of two vastly different antiagglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. Results show that alcohol cosurfactants may help with antiagglomeration when traditional antiagglomerants alone are ineffective. Specifically, as low as 0.5 wt. % methanol cosurfactant used in this study is shown to be effective in antiagglomeration. Without the cosurfactant there will be agglomeration independent of the AA concentration. To our knowledge, this is the first report of alcohol cosurfactants in hydrate antiagglomerants. It is also shown that a rhamnolipid biosurfactant is effective down to only 0.5 wt. % in such mixtures, yet a quaternary ammonium chloride salt, i. e., quat, results in hydrate slurries down to 0.01 wt. %. However, biochemical surfactants are less toxic and biodegradable, and thus their use may prove beneficial even if at concentrations higher than chemical surfactants.