Experimental and density functional theory computational evaluation of poly(N-vinyl caprolactam-co-butyl methacrylate) kinetic hydrate inhibitors

Natural gas hydrate inhibitor has been serving the oil and gas industry for many years. The development and search for new inhibitors remain the focus of research. In this study, the solution polymerization method was employed to prepare poly(N-vinyl caprolactam-co-butyl methacrylate)(P(VCap-BMA)), as a new kinetic hydrate inhibitor(KHI). The inhibition properties of P(VCap-BMA) were investigated by tetrahydrofuran(THF) hydrate testing and natural gas hydrate forming and compared with the commercial KHIs. The experiment showed that PVCap performed better than copolymer P(VCap-BMA). However,low doses of methanol or ethylene glycol are compounded with KHIs. The compounding inhibitors show a synergistic inhibitory effect. More interesting is the P(VCap-BMA)-methanol system has a better inhibitory effect than the PVCap-methanol system. 1% P(VCap-BMA) + 5% methanol presented the best inhibiting performance at subcooling 10.3 °C, the induction time of natural gas hydrate was 445 min.Finally, the interaction between water and several dimeric inhibitors compared by natural bond orbital(NBO) analyses and density functional theory(DFT) indicated that inhibitor molecules were able to form the hydrogen bond with the water molecules, which result in gas hydrate inhibition. These exciting properties make the P(VCap-BMA) compound hydrate inhibitor promising candidates for numerous applications in the petrochemical industry.

A Study on Inhibitors for the Prevention of Hydrate Formation in Gas Transmission Pipeline

Gas Hydrate is usually formed during the transportation and treatment of oil and gas, resulting in the plugging of gas pipeline and equipment. Three thermodynamic calculation formulas are analyzed to deal with this problem. The lowering of the freezing point of the inhibitors △T is used to calculate the formation temperature of natural gas hydrates. This is considered to be a good approach because it is not limited by what kind and what concentration of inhibitors one uses. Besides, the rate of lowering of the freezing point could be easily measured. The result of testing methanol and mono-ethylene glycol in a reactor shows that adding 10% inhibitors to the reactor can prevent the hydrates formation. Kinetic inhibitors are favored in the present research. They are divided into two types, polymer and surface-active agents. Their characteristics, mechanisms, and application prospect are separately discussed. Polymer inhibitors exhibit better efficiency. The result of field application of VC-713 inhibiter is also given in this article. In practice, the combination of thermodynamic inhibitors and kinetic inhibitors gives better result.

Experimental study of hydrogen sulfide hydrate formation: Induction time in the presence and absence of kinetic inhibitor

In this paper, the effect of adding different concentrations of kinetic inhibitors on the induction time of hydrogen sulfide hydrate formation in a reactor equipped with automatic adjustable temperature controller is studied. A novel method namely ＂sudden cooling＂ is used for performing the relevant measurements, in which the induction time of H2S hydrate in the presence/absence of PVP and L-tyrosine with different concentrations （100, 500, and 1000 ppm） is determined. As a result, PVP with the concentration of 1000 ppm in aqueous solution is detected as a more suitable material for increasing the induction time of H2S hydrate formation among the investigated kinetic hydrate inhibitors.

Insights into kinetic inhibition effects of MEG,PVP,and L-tyrosine aqueous solutions on natural gas hydrate formation

It is necessary to understand all the prerequisites, which result in gas hydrate formation for safe design and control of a variety of processes in petroleum industry. Thermodynamic hydrate inhibitors (THIs) are normally used to preclude gas hydrate formation by shifting hydrate stability region to lower temperatures and higher pressures. Sometimes, it is difficult to avoid hydrate formation and hydrates will form anyway. In this situation, kinetic hydrate inhibitors (KHIs) can be used to postpone formation of gas hydrates by retarding hydrate nucleation and growth rate. In this study, two kinetic parameters including natural gas hydrate formation induction time and the rate of gas consumption were experimentally investigated in the presence of monoethylene glycol (MEG), L-tyrosine, and polyvinylpyrrolidone (PVP) at various concentrations in aqueous solutions. Since hydrate formation is a stochastic phenomenon, the repeatability of each kinetic parameter was evaluated several times and the average values for the hydrate formation induction times and the rates of gas consumption are reported. The results indicate that from the view point of hydrate formation induction time, 2 wt% PVP and 20 wt% MEG aqueous solutions have the highest values and are the best choices. It is also interpreted from the results that from the view point of the rate of gas consumption, 20 wt% MEG aqueous solution yields the lowest value and is the best choice. Finally, it is concluded that the combination of PVP and MEG in an aqueous solution has a simultaneous synergistic impact on natural gas hydrate formation induction time and the rate of gas consumption. Furthermore, a semi-empirical model based on chemical kinetic theory is applied to evaluate the hydrate formation induction time data. A good agreement between the experimental and calculated hydrate formation induction time data is observed.

Kinetic hydrate inhibitor performance of new copolymer poly(N-vinyl-2-pyrrolidone-co-2-vinyl pyridine)s with TBAB

In oil and gas field, the application of kinetic hydrate inhibitors （KHIs） independently has remained problematic in high subcooling and high water-cut situation. One feasible method to resolve this problem is the combined use of KHIs and some synergists, which would enhance KHIs’ inhibitory effect on both hydrate nucleation and hydrate crystal growth. In this study, a novel kind of KHI copolymer poly（N-vinyl-2-pyrrolidone-co-2-vinyl pyridine）s （HGs） is used in conjunction with TBAB to show its high performance on hydrate inhibition. The performance of HGs with different monomer ratios in structure II tetrahydrofuran （THF） hydrate is investigated using kinetic hydrate inhibitor evaluation apparatus by step-cooling method and isothermal cooling method. With the combined gas hydrate inhibitor at the concentration of 1.0 wt%, the induction time of 19 wt% THF solution could be prolonged to 8.5 h at a high subcooling of 6℃. Finally, the mechanism of HGs inhibiting the formation of gas hydrate is proposed.

Leaching kinetics of ionic rare-earth in ammonia-nitrogen wastewater system added with impurity inhibitors

Ammonia-nitrogen wastewater is produced during the dressing and smelting process of rare-earth ores.Such wastewater includes a very high concentration of NH4＋, as well as other ions（e.g., NH4＋, RE3＋, Al3＋, Fe3＋, Ca2＋, Cl–, and Si O32–） with a p H of 5.4–5.6.Its direct discharge will pollute, yet it can be recycled and used as a leaching reagent for ionic rare-earth ores.In this study, leaching kinetics studies of both rare earth ions and impurity ion Al3＋ were conducted in the ammonia-nitrogen wastewater system with the aid of impurity inhibitors.Results showed that the leaching process of rare-earth followed the internal diffusion kinetic model.When the temperature was 298 K and the concentration of NH4＋ was 0.3 mol/L, the leaching reaction rate constant of ionic rare-earth was 1.72 and the apparent activation energy was 9.619 k J/mol.The leaching rate was higher than that of conventional leaching system with ammonium sulfate, which indicated that ammonia-nitrogen wastewater system and the addition of impurity inhibitors could promote ionic rare-earth leaching.The leaching kinetic process of impurity Al3＋ did not follow either internal diffusion kinetic model or chemical reaction control, but the hybrid control model which was affected by a number of process factors.Thus, during the industrial production the leaching of impurity ions could be reduced by increasing the concentration of impurity inhibitors, reducing the leaching temperature to a proper range, accelerating the seepage velocity of leaching solution, or increasing the leaching rate of rare earths.

High efficient development of green kinetic hydrate inhibitors via combined molecular dynamic simulation and experimental test approach

The development of environmental friendly low dose hydrate inhibitors like kinetic hydrate inhibitors(KHIs)is of great significance for the flow assurance in oil&gas production and transportation.In this work,a combined molecular dynamic simulation and experimental verification approach was adopted to increase the efficiency of KHIs development.The inhibition effect of a series of copolymers(N-vinylpyrrolidone and N-acrylate)on hydrate growth was studied by using both molecular dynamics simulation and experimental approaches.The simulation results demonstrated that introduction of hydrophobic ester and butyl group in PVP is beneficial for the inhibition.The length of the alkyl chain of ester group played an important role in improving inhibition performance.PVP-A,the one being introduced butyl ester group into PVP gets the best inhibition effect.In addition,inhibitors can restrict methane bubbles to re-dissolve into the liquid phase,thereby inhibiting the growth of methane hydrate.Increasing the interaction between KHIs and methane can also improve the inhibitory effect of KHIs.The experimental results confirm the reliability of the molecular dynamics simulation.

Synthesis and application of a novel combined kinetic hydrate inhibitor

In oil and gas exploration and transportation, low dosage hydrate inhibitors （LDHIs） are more favorably utilized to inhibit the formation of hydrates than thermodynamic inhibitors （THs） as a trend. However, there are no industrial products of LDHIs available domestically, and the corresponding application experience is in urgent need. In this paper, a combined hydrate inhibitor （HY-1） was synthesized after a series of reaction condition optimization, and its performance on THF hydrate inhibition was investigated using kinetic hydrate inhibitor evaluation apparatus with 6 cells bathing in air. The results show that when the reaction temperature is 60℃, the reaction time is 6 h, and the monomer： solvent ratio is 1：2, the product has the best kinetic hydrate inhibitor performance on THF hydrate. On these bases, the scale-up production of this combined hydrate inhibitor was carried out. Although the scale-up product （HY-10） performs less effectively on the THF hydrate inhibition than HY-1, it functions better than a commercial product （Inhibex501） during in-house tests. HY-10 was successfully applied to the gas production process. Field trials in northem Shaanxi PetroChina Changqing Oilfield Company （PCOC） show that 2 wt% of HY-10 is effective on natural gas hydrate inhibition. It is found through economic analysis that the use of HY-10 has obvious economi- cal advantage over methanol and Inhibex501.