An investigation into the laboratory method for the evaluation of the performance of kinetic hydrate inhibitors using superheated gas hydrates

Kinetic hydrate inhibitors (KHIs) are used to prevent gas hydrate formation in gas and oilfield operations. Recently, a new KHI test method was reported in which hydrates are formed and re-melted just above the equilibrium temperature, before the fluids are re-cooled and the performance of the chemical as a KHI is determined. The method, which we have called the superheated hydrate test method, is claimed to be more reliable for KHI ranking in small equipment, giving less scattering in the hold time data due to avoiding the stochastic nature of the first hydrate formation. We have independently investigated this superheated hydrate test method in steel and sapphire autoclave tests using a gas mixture forming Structure II hydrates and a liquid hydrocarbon phase, which was necessary for satisfactory results. Our results indicate that hold times are shorter than using non-superheated hydrate test methods, but they are more reproducible with less scattering. The reduced scattering occurs in isothermal or slow ramping experiments even when the hydrates are melted at more than 10 °C above the equilibrium temperature (T_eq). However, if a rapid cooling method is used, the improved reproducibility is retained when melting hydrate at 2.4 °C above T_eq but lost when warming to 8.4 °C above T_eq. Using the ramping test method, most, but not all the KHIs tested agreed with the same performance ranking obtained using traditional non-superheated hydrate test methods. This may be related to the variation in the dissociation temperature of gas hydrates with different KHIs and different KHI inhibition mechanisms. Results also varied between different size autoclave equipments.     

Quantitative analysis of gas hydrates using Raman spectroscopy

A calibration protocol to quantify the compositional information of gas hydrates using Raman spectroscopy is proposed. Structure I pure CH₄‐, CO₂‐ and C₂H₆‐hydrates in their deuterated and hydrogenated forms with known cage occupancies were investigated by Raman spectroscopy. Raman scattering cross sections of CH₄ in the large and small cages were found to be very similar, but not identical. Some C₂H₆ bands of C₂H₆‐hydrate were tentatively reassigned or newly reported and assigned. Our results show that the relative cross sections of guest vibrational modes in the deuterated hydrate are in agreement with those in the hydrogenated hydrate, whereas they are considerably different from those in fluid phase. Using our Raman quantification factors, the relative cage occupancies can now be determined more reliably in CH₄‐hydrates. Moreover, with additional assumptions, the absolute cage occupancies, the bulk guest composition and hydration number of pure or mixed gas hydrates become accessible by Raman spectroscopy. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2155–2167, 2013     

Thermodynamic stability, spectroscopic identification and cage occupation of binary CO2 clathrate hydrates

The hydrate phase behavior of CO₂/3-methyl-1-butanol (3M1B)/water, CO₂/tetrahydrofuran (THF)/water and CO₂/1,4-dioxane (DXN)/water was investigated using both a high-pressure equilibrium viewing cell and a kinetic pressure-temperature measurement system with a constant volume. The dissociation pressures of CO₂/3M1B/water were identical to those of pure CO₂ hydrate, indicating that CO₂ is not acting as a help gas for structure H hydrate formation with 3M1B, thus the formed hydrate is pure CO₂ structure I hydrate. The CO₂ molecules could be encaged in small cages of the structure II hydrate framework formed with both of THF and DXN. For a stoichiometric ratio of 5.56 mol% THF, we found a large shift of dissociation boundary to lower pressures and higher temperatures from the dissociation conditions of pure CO₂ hydrate. From the measurements using the kinetic pressure-temperature system, it was found that the solid binary hydrate samples formed from off-stoichiometric THF and DXN aqueous solutions are composed of pure CO₂ hydrate with a hydrate number n=7.0 and THF/CO₂ and DXN/CO₂ binary hydrates with a molar ratio of xCO₂·THF·17H₂O and xCO₂·DXN·17H₂O, respectively. The X-ray diffraction was used to identify the binary hydrate structure and Raman spectroscopy was measured to support the phase equilibrium results and to investigate the occupation of CO₂ molecules in the cages of the hydrate framework.     

Notes on the dissolution rate of gas hydrates in undersaturated water

An elementary model for the dissolution of pure hydrate in undersaturated water is proposed that combines intrinsic decomposition within a desorption film and the subsequent diffusion of the released hydrate guest species into bulk water. Applying the proposed approach to recently published measurements of the decomposition rates of methane (CH₄) and carbon dioxide (CO₂) hydrates in deep seawater suggests that the concentration of the hydrate guest species at the interface between desorption film and diffusive boundary layer may be much lower than ambient solubility. Calculations, however, fail to account for the observed proportionality of decomposition rate with solubility for both CH₄ and CO₂ hydrates. This may indicate a limitation in the range of applicability of published formulas for intrinsic hydrate decomposition rates.     

芬兰水管理和废水净化

介绍了芬兰水专项计划产生的背景,芬兰水资源管理和废水净化受到芬兰政府支持和机构间多方合作。详细阐述了芬兰水资源保护和废水处理的各种实施方案,希望对我国水管理及废水处理能有所借鉴。     

某南水北调水源水厂净水工艺设计

某城区供水采用南水北调中线水源。根据该城区现状,以及进水水质条件和出水水质要求,经技术经济比较确定了预氧化-常规处理-预留深度处理的工艺方案。工程运行结果表明,出水水质完全符合GB 5749—2006《生活饮用水卫生标准》的要求。     

Reductant-assisted polydopamine-modified membranes for efficient water purification

Surface engineering with polydopamine coatings has been considered a promising surface functionalisation tool.However,it is difficult to control the self-polymerisation for polydopamine formation,which usually causes severe interparticle aggregation.In this study,polydopamine self-polymerisation was controlled by adjusting its reducing environment using a reductant(NaBH4)to fabricate mixed cellulose ester(MCE)/polydopamine membranes.An oxidising environment using NaIO4 was additionally tested as the control.The results showed that a thin polydopamine coating with small polydopamine particles was formed on the skeleton frameworks of the MCE membrane with NaBH4,and the self-polymerisation rate was suppressed.The polydopamine coating formed in the reducing environment facilitated excellent water transport performance with a water permeance of approximately 400 L·m^?2·h^?1·bar^?1 as well as efficient organic foulant removal with a bovine serum albumin rejection of approximately 90%.In addition,the polydopamine coating with NaBH4 exhibited both excellent chemical stability and anti-microbial activity,demonstrating the contribution of the reducing environment to the performance of the MCE/polydopamine membranes.It shows significant potential for use in water purification.     

Thermodynamic consistency test for experimental data of water content of methane

Accurate knowledge of the water content of natural gases is an important factor to estimate the gas hydrate, ice, and condensed water formation conditions. However, the experimental data regarding the water content of gases in equilibrium with the gas hydrate, ice, or liquid water (near gas hydrate or ice formation region) are limited. This is partly because of the fact that concentration of water in the gaseous phase in equilibrium with gas hydrate, ice or liquid water (near gas hydrate or ice formation region) is very low considering that reaching the equilibrium conditions near and inside gas hydrate or ice formation region is time consuming process. The measurement difficulties may consequently result in generating unreliable experimental data. This work aims at performing a thermodynamic consistency test based on area approach to study the reliability of some experimental data reported in the literature on the water content of methane (the main component of natural gases) in equilibrium with the gas hydrate, ice, or liquid water (near gas hydrate or ice formation region). A discussion is made on the studied experimental data according to the performed consistency test. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

Thermodynamic model for predicting phase equilibria of simple clathrate hydrates of refrigerants

In this communication, a thermodynamic model is presented for the study of the phase equilibria of clathrate hydrates of simple refrigerants. The van der Waals–Platteeuw solid solution theory is used to model the hydrate phase while it is assumed that vapor phase is an ideal gas of refrigerant ignoring its water content and the aqueous phase is considered as pure water (activity coefficient=1) ignoring aqueous solubility. The results through this model are successfully compared with the experimental data reported in the literature for clathrate hydrates of four refrigerants namely C₂H₂F₄ (1, 1, 1, 2-tetrafluoroethane or HFC-134a or R-134a), C₂H₄F₂ (1, 1-difluoroethane or HFC-152a or R-152a), CH₂F₂ (difluoromethane or HFC-32 or R-32), and C₂H₃Cl₂F (1,1-dichloro-1-fluoroethane or HCFC-141b or R-141b).     

Nucleation curves of model natural gas hydrates on a quasi‐free water droplet

Heterogeneous nucleation probability distributions of gas hydrates on a water droplet that was supported by inert and immiscible perfluorocarbon oil, perfluorodecalin is studied. The guest gas used was a mixture of 90 mol % methane and 10 mol % propane. The probability distribution was measured using a high pressure automated lag time apparatus under the guest gas pressure range of 6.7–12.5 MPa and the cooling rate range of 0.002–0.02 K/s. Nucleation curves were derived for unit area of water surface. The nucleation rate per unit area of water surface that was contained in a glass sample cell, which differed significantly from that on a quasi‐free water droplet, is also derived. It is concluded that the nucleation curves in the presence of a solid wall should be normalized to the unit length of the three‐phase line at which water, guest gas, and the solid wall meet. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2611–2617, 2015     

纯化天然气水合物螺旋分离器流场与性能分析

基于海洋天然气水合物固态流化开采方法的井下原位除砂提纯回填工艺,本文结合试采所得水合物浆体特征,设计用于解决设备磨损、储层坍塌等问题的井下除砂螺旋分离器,利用CFD数值模拟方法研究了入口速度和水合物体饱和度对井下除砂螺旋分离器流场和性能的影响,得到了随着入口速度增加,流场中流体的速度急剧增大,特别是切向速度、分离效率增加。当分离效率为70%以上,分离器内压降急剧增大,表明分离器内部的能量损耗不断增加;随着入口水合物体积分数的增加,螺旋分离器内流场变化微小,水合物分离效率降低,砂分离效率增加;分离效率为80%以上,压降逐渐降低。说明该分离器的最佳操作区为入口速度范围为3～5m/s,水合物入口体积分数15%以下。研究结果表明：本螺旋分离器具有极佳的除砂效果;切向速度是决定分离器分离性能的关键速度,处理量的增大有利于水合物的提纯;海底水合物储层中水合物饱和度变化对螺旋分离器分离效率具有一定的影响,但螺旋分离器对其具有一定的适应能力;揭示了水合物井下螺旋分离器除砂的分离机理,为其设计提供了一定的依据,为海洋水合物储层开采防砂提了一种新的技术及装备。     

电去离子净水技术的新进展

综合介绍了美国Ｉｏｎｐｕｒｅ＾ＴＭ加拿大Ｅ－Ｃｅｌｌ＾ＴＭ这两种电去离子净水装置的性能及应用,并讨论了我国在研究离子交换树脂电再生技术及开发电去离子净水产品方面的进展。从技术水平、市场开发前景和我国其他诸多因素的实际情况出发,建议优先开发作者依据ＥＤＩ中自再生原理发明的离子交换树脂的电再生技术。     

Synthesis and characterization of polyphenylaminophosphazene and fluorinated polyarylaminophosphazene

Two polyarylaminophosphazenes, poly[bis(phenylamino)phosphazene] (PBAP) and poly[bis(p‐trifluoroethoxyphenylamino)phosphazene] (PBTAP), were successfully synthesized by ring‐opening polymerizations and nucleophilic substitution reactions. Their chemical structures, thermal properties, and surface properties were investigated by NMR, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and water contact angles (WCA). The results indicate that the glass‐transition temperature (T_g), thermal stability, and WCAs of PBAP and PBTAP presented obviously differences; this suggested that PBTAP possessed the lower T_g and higher contact angle than PBAP. This was attributed to the influence of trifluoroethoxy at the para position of aniline. TGA measurements indicated that PBAP possessed a higher thermal stability than PBTAP; this was attributed to the strong electron‐withdrawing influence of the trifluoroethoxy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42542.     

Addressing water scarcity: cationic polyelectrolytes in water treatment and purification

Synthetic cationic polyelectrolytes (CPEs) serve as coagulation and flocculation agents in wastewater treatment due to a synergy of inherent electrostatic interactions and hydrophilic properties. In wastewater treatment, CPEs act as coagulation and flocculation agents to aggregate impurities and enable water purification. New health and environmental‐related regulations provide motivation for government agencies and industrial companies to reuse wastewater. Chemical structure, molecular weight, charge density and functionality of CPEs provide tailorability for specific purification needs. Cationic polyacrylamides, ammonium‐based polymers, poly(allyldimethyl‐ammonium chloride) and epichlorohydrin/dimethylamine‐based polymers are the most common CPEs used as coagulation and flocculation agents because they are economical and water soluble with tunable charge densities at high molecular weights. Free radical polymerization, step‐growth polymerization and post‐polymerization modification methods afford each polymer system. This review highlights recent advancements in synthetic methods to yield CPEs, structure?property relationships as related to flocculation efficiency and a summary of their toxicity and environmental impact. © 2018 Society of Chemical Industry     

Evidence of liquid water formation during methane hydrates dissociation below the ice point

Dissociation of small methane hydrate samples formed from water droplets of size 0.25-2.5 mm has been investigated below the ice melting point in the temperature range of 240-273 K, where the self-preservation effect is observed for bulk hydrates. The experiments included optical microscopy observations combined with P-T measurements of the dissociation conditions for the methane hydrates. For the first time, the formation of supercooled liquid water during the hydrate dissociation was reliably detected in the temperature range of 253-273 K. The formation of the liquid phase was visually observed. The induction time of the ice nucleation for the metastable liquid water depended from the dissociation temperature and a size of water droplets formed during the hydrate dissociation. It was found that in the temperature range of 253-273 K values of the dissociation pressure for the small hydrate samples fall on the extension of the water-hydrate-gas equilibrium curve into the metastable region where supercooled water exist. The average molar enthalpy of 51.7 kJ/mol for the dissociation of the small methane hydrate samples in the temperature range of 253-273 K was calculated using Clausius-Clapeyron equation. This value agrees with the enthalpy of dissociation of bulk methane hydrates into water and gas at temperatures above 273 K.     

“三法净水”与JR-EDR技术处理焦化循环水

中煤九鑫焦化有限责任公司现有电厂循环水、化产循环水及化产低温循环水3个循环水场,产生污水70 m3/h,为节水减排,采用三法净水专利技术与JR-EDR(新型频繁倒极电渗析)技术组合工艺对污水进行处理回用。与传统的混凝过滤技术相比,三法净水技术不仅能去除水中的浊度、悬浮物,而且能去除硬度、胶体、总磷、COD等,为后续JR-EDR脱盐设备提供较好的进水条件。JR-EDR脱盐工艺作为一种物理化学反应过程进行脱盐。组合工艺的联用有效提高循环水系统水质的同时减少了排污量。     

天然气水合物优化合成实验研究

水合物储运技术实用化的进程中,如何提高水合物制备效率,实现高密度的储存是最为关键的问题。文中对此应用新型雾化系统对气水合物的强化合成技术进行了实验研究。结果表明:压力提高对水合物生长加速作用明显;活性剂组分和雾化方式提供了最优的气液传质条件,极大地加快了溶解、成核及生长过程,其整体反应速度提高了1倍以上,最终含气体积比也显著提高;分解水重复生成、水合物晶种的投入也能极大加快成核过程,缩短诱导期,从而提高反应速率。