Ethylene Glycol as Gas Hydrate Stabilising Substance

2015 ◽  
Author(s):  
Anne Schulz ◽  
Heike Strauß
Keyword(s):  
High Pressure ◽  
Natural Gas ◽  
Ethylene Glycol ◽  
Gas Hydrates ◽  
Gas Hydrate ◽  
Methane Hydrate ◽  
Sea Water ◽  
Drilling Fluid ◽  
Sodium Dodecyl ◽  
Gas Hydrate Formation

Gas hydrates are solid substances consisting of water and gas which are stable under high pressure and low temperature conditions. After Davy discovered chlorine hydrate in 1810, gas hydrates from natural gas were found to be the reason for gas pipeline plugging in 1934 by Hammerschmidt. In 1965, the Russian scientist Makogon discovered natural gas hydrate deposits. This was the beginning of research in the geological occurrence of the gas hydrates. Today, hundreds of gas hydrate wells for exploration have been drilled all over the world in the permafrost and deep sea regions. Several big projects for gas hydrate research and exploration have been financed by Japan, India, Korea, China and the USA. It is assumed that the amount of carbon in natural gas hydrates is twice the amount present in oil, gas and coal together. This makes them interesting as a future energy source. To drill into horizontal layers filled with gas hydrates in the pores, directional wells are needed. To achieve an adequate cutting transport, a high performance drilling fluid has to be used instead of sea water. The drilling fluid must be able to keep the gas hydrate reservoir stable while drilling and prevent the formation of secondary gas hydrates in the liquid. Moreover, the gas hydrate cuttings should not dissociate on their way to the surface. To avoid altering of the drilling fluid due to water and gas produced as a result of gas hydrate dissociation, cuttings should be kept stable to separate them from the fluid like any other rock cuttings by the surface equipment. To prevent gas hydrate formation, thermodynamic inhibitors, like salt, glycols or methanol are used. Also, kinetic inhibitors are added to the drilling fluid to prevent gas hydrate agglomeration and formation for a period of time. Well known kinetic inhibitors are polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyvinylcaprolactam (PVCap). Although ethylene glycol (EG) is seen as a thermodynamic inhibitor for gas hydrates, it is shown in this study that it is able to stabilize methane hydrate significantly. For the investigation, a high pressure cell with pressures up to 8.5 MPa was used. The equilibrium point of methane hydrate was detected. Solutions with PVP, PEG, hydroxyethylcellulose (HEC), Sodium dodecyl sulfate (SDS) and a kinetic inhibitor containing EG were tested (concentrations from 1 to 10 wt.‰). PVP, PEG and HEC could not stabilize gas hydrates at the test condition. SDS showed both a stabilizing and promoting effect. EG can significantly stabilize gas hydrates.

MRI Visualization of Spontaneous Methane Production From Hydrates in Sandstone Core Plugs When Exposed to CO2

SPE Journal ◽  
2008 ◽  
Vol 13 (02) ◽  
pp. 146-152 ◽  
Author(s):  
Arne Graue ◽  
B. Kvamme ◽  
Bernie Baldwin ◽  
Jim Stevens ◽  
James J. Howard ◽  
...  
Keyword(s):  
Natural Gas ◽  
Gas Hydrates ◽  
Gas Hydrate ◽  
Methane Production ◽  
Methane Hydrate ◽  
Co2 Storage ◽  
Natural Gas Hydrate ◽  
Hydrate Dissociation ◽  
Natural Gas Hydrates ◽  
The Stability

Summary Magnetic resonance imaging (MRI) of core samples in laboratory experiments showed that CO2 storage in gas hydrates formed in porous rock resulted in the spontaneous production of methane with no associated water production. The exposure of methane hydrate in the pores to liquid CO2 resulted in methane production from the hydrate that suggested the exchange of methane molecules with CO2 molecules within the hydrate without the addition or subtraction of significant amounts of heat. Thermodynamic simulations based on Phase Field Theory were in agreement with these results and predicted similar methane production rates that were observed in several experiments. MRI-based 3D visualizations of the formation of hydrates in the porous rock and the methane production improved the interpretation of the experiments. The sequestration of an important greenhouse gas while simultaneously producing the freed natural gas offers access to the significant amounts of energy bound in natural gas hydrates and also offers an attractive potential for CO2 storage. The potential danger associated with catastrophic dissociation of hydrate structures in nature and the corresponding collapse of geological formations is reduced because of the increased thermodynamic stability of the CO2 hydrate relative to the natural gas hydrate. Introduction The replacement of methane in natural gas hydrates with CO2 presents an attractive scenario of providing a source of abundant natural gas while establishing a thermodynamically more stable hydrate accumulation. Natural gas hydrates represent an enormous potential energy source as the total energy corresponding to natural gas entrapped in hydrate reservoirs is estimated to be more than twice the energy of all known energy sources of coal, oil, and gas (Sloan 2003). Thermodynamic stability of the hydrate is sensitive to local temperature and pressure, but all components in the hydrate have to be in equilibrium with the surroundings if the hydrate is to be thermodynamically stable. Natural gas hydrate accumulations are therefore rarely in a state of complete stability in a strict thermodynamic sense. Typically, the hydrate associated with fine-grain sediments is trapped between low-permeability layers that keep the system in a state of very slow dynamics. One concern of hydrate dissociation, especially near the surface of either submarine or permafrost-associated deposits, is the potential for the release of methane to the water column or atmosphere. Methane represents an environmental concern because it is a more aggressive (~25 times) greenhouse gas than CO2. A more serious concern is related to the stability of these hydrate formations and its impact on the surrounding sediments. Changes in local conditions of temperature, pressure, or surrounding fluids can change the dynamics of the system and lead to catastrophic dissociation of the hydrates and consequent sediment instability. The Storegga mudslide in offshore Norway was created by several catastrophic hydrate dissociations. The largest of these was estimated to have occurred 7,000 years ago and was believed to have created a massive tsunami (Dawson et al. 1988). The replacement of natural gas hydrate with CO2 hydrate has the potential to increase the stability of hydrate-saturated sediments under near-surface conditions. Hydrocarbon exploitation in hydrate-bearing regions has the additional challenge to drilling operations of controlling heat production from drilling and its potential risk of local hydrate dissociation (Yakushev and Collett 1992). The molar volume of hydrate is 25-30% greater than the volume of liquid water under the same temperature-pressure conditions. Any production scenario for natural gas hydrate that involves significant dissociation of the hydrate (e.g., pressure depletion) has to account for the release of significant amounts of water that in turn affects the local mechanical stress on the reservoir formation. In the worst case, this would lead to local collapse of the surrounding formation. Natural gas production by CO2 exchange and sequestration benefits from the observation that there is little or no associated liquid water production during this process. Production of gas by hydrate dissociation can produce large volumes of associated water, and can create a significant environmental problem that would severely limit the economic potential. The conversion from methane hydrate to a CO2 hydrate is thermodynamically favorable in terms of free energy differences, and the phase transition is coupled to corresponding processes of mass and heat transport. The essential question is then if it is possible to actually convert methane hydrate as found in sediments to CO2 hydrate. Experiments that formed natural gas hydrates in porous sandstone core plugs used MRI to monitor the dynamics of hydrate formation and reformation. The paper emphasizes the experimental procedures developed to form the initial natural gas hydrates in sandstone pores and the subsequent exchange with CO2 while monitoring the dynamic process with 3D imaging on a sub millimetre scale. The in-situ imaging illustrates the production of methane from methane hydrate when exposed to liquid CO2 without any external heating.

Natural Gas Hydrate Formation and Decomposition in the Presence of Kinetic Inhibitors. 1. High Pressure Calorimetry

2011 ◽  
Vol 25 (10) ◽  
pp. 4392-4397 ◽  
Author(s):  
Nagu Daraboina ◽  
John Ripmeester ◽  
Virginia K. Walker ◽  
Peter Englezos
Keyword(s):  
High Pressure ◽  
Natural Gas ◽  
Gas Hydrate ◽  
Hydrate Formation ◽  
Natural Gas Hydrate ◽  
Gas Hydrate Formation

Investigation of Drilling Problems in Gas Hydrate Formations

2008 ◽  
Author(s):  
Catalin Teodoriu ◽  
Gioia Falcone ◽  
Amodu Afolabi
Keyword(s):  
Gas Hydrates ◽  
Gas Hydrate ◽  
Oil And Gas ◽  
Drilling Fluid ◽  
Hydrate Formation ◽  
Oil And Gas Industry ◽  
Lessons Learned ◽  
Drilling Fluids ◽  
Drilling Mud ◽  
Gas Hydrate Formation

Gas hydrates are ice-like crystalline systems made of water and methane that are stable under high pressure and low temperature conditions. Gas hydrates have been identified as strategic resources and may surpass all known oil and gas reserves combined. However, these resources will become reserves only if the gas contained therein can be produced economically. In the oil and gas industry, gas hydrates may be encountered while drilling sediments of the subsea continental slopes and in the subsurface of permafrost regions. They also represent a flow assurance issue, as they may form in the well and in the flowlines, causing blockages. Deepwater drilling programmes have experienced problems when encountering gas hydrate formations. A major issue is that of phase transition, where gas hydrate goes from a solid state to dissociated gas and water, as there are rapid changes in fluid volumes and pressure. This can cause drilling equipment failure, borehole instability and formation collapse. After dissociation of water and gas, hydrates may be prevented from forming in the well by using appropriate inhibitors in the drilling mud. There is a need to develop fluids specifically for drilling through gas hydrate formations, either to unlock the unconventional reserves trapped in the crystalline gas hydrate structures or to safely reach underlying conventional reserves. To drill wells in a gas hydrate formation, a conductor casing is needed to allow close loop circulation of the mud, if different from seawater. The search for the ideal mud for drilling through gas hydrate formations must start with a review of past experiences worldwide and of the lessons learned. This paper presents a review of the problems encountered while drilling through gas hydrate formations. It identifies the key requirements for drilling fluids, based on the interaction between the drill bit, the drilling fluid and the formation. An evaluation of the environmental risk associated with drilling through gas hydrate formations is also presented.

scholarly journals Gas Hydrate Formation Phase Boundary Behaviour of Synthetic Natural Gas System of the Keta Basin of Ghana

2017 ◽  
Vol 10 (1) ◽  
pp. 64-72 ◽  
Author(s):  
Eric Broni-Bediako ◽  
Richard Amorin ◽  
Cornelius B. Bavoh
Keyword(s):  
Natural Gas ◽  
Phase Boundary ◽  
Gas Hydrates ◽  
Gas Hydrate ◽  
Hydrate Formation ◽  
Simulation Software ◽  
Gas Composition ◽  
Synthetic Natural Gas ◽  
Gas Hydrate Formation ◽  
Formation Phase

Background:Gas hydrates are considered as a major threat to the oil and gas flow assurance industry. At high pressure and low temperature conditions, gas hydrates form in pipelines and production facilities leading to pipeline blockages, high removal cost, environmental hazards and loss of lives. For a successful prevention of gas hydrate formation, predicting the hydrate formation phase boundary of hydrocarbon fluid composition becomes very necessary.Objective and Method:In this study, computer simulation software called PVTSim was used to predict hydrate formation phase boundary of synthetic natural gas composition of the Keta basin of Ghana at pressure and temperature ranges of 43.09 bar - 350 bar and 12.87 °C - 27.29 °C respectively. The effect of changes in natural gas composition (N2and H2S) and the presence of four commonly used thermodynamic gas hydrate inhibitors (methanol, ethanol, diethylene glycol and monoethylene glycol) on the hydrate formation phase boundary is also discussed. Prior to the study, the accuracy of PVTSim was validated with the hydrate formation phase data in literature.Results and Conclusion:Results suggested that the hydrate formation phase boundary decreased with increasing N2composition and increased with increasing H2S composition, suggesting that, the presence of H2S increases the threat of hydrate formation. However, a reduction in hydrate formation threat was observed in the presence of all four commonly used gas hydrate thermodynamic inhibitors with methanol demonstrating the highest inhibition effect.

Thermodynamic Modelling of Gas Hydrate Formation in the Presence of Inhibitors and the Consideration of their Effect

2014 ◽  
Vol 14 (1) ◽  
pp. 45
Author(s):  
Peyman Sabzi ◽  
Saheb Noroozi
Keyword(s):  
Gas Hydrates ◽  
Gas Hydrate ◽  
Low Temperatures ◽  
Hydrate Formation ◽  
Transportation Systems ◽  
Flow Lines ◽  
Main Approach ◽  
Efficient Inhibitor ◽  
System A ◽  
Gas Hydrate Formation

Gas hydrates formation is considered as one the greatest obstacles in gas transportation systems. Problems related to gas hydrate formation is more severe when dealing with transportation at low temperatures of deep water. In order to avoid formation of Gas hydrates, different inhibitors are used. Methanol is one of the most common and economically efficient inhibitor. Adding methanol to the flow lines, changes the thermodynamic equilibrium situation of the system. In order to predict these changes in thermodynamic behavior of the system, a series of modelings are performed using Matlab software in this paper. The main approach in this modeling is on the basis of Van der Waals and Plateau's thermodynamic approach. The obtained results of a system containing water, Methane and Methanol showed that hydrate formation pressure increases due to the increase of inhibitor amount in constant temperature and this increase is more in higher temperatures. Furthermore, these results were in harmony with the available empirical data.Keywords: Gas hydrates, thermodynamic inhibitor, modelling, pipeline blockage

scholarly journals Rapid Gas Hydrate Formation—Evaluation of Three Reactor Concepts and Feasibility Study

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3615
Author(s):  
Florian Filarsky ◽  
Julian Wieser ◽  
Heyko Juergen Schultz
Keyword(s):  
Gas Hydrates ◽  
Gas Hydrate ◽  
Hydrate Formation ◽  
Synthetic Natural Gas ◽  
Operation Conditions ◽  
Gas Hydrate Formation ◽  
Gas Conditioning ◽  
And Storage ◽  
Economic Considerations ◽  
High Storage

Gas hydrates show great potential with regard to various technical applications, such as gas conditioning, separation and storage. Hence, there has been an increased interest in applied gas hydrate research worldwide in recent years. This paper describes the development of an energetically promising, highly attractive rapid gas hydrate production process that enables the instantaneous conditioning and storage of gases in the form of solid hydrates, as an alternative to costly established processes, such as, for example, cryogenic demethanization. In the first step of the investigations, three different reactor concepts for rapid hydrate formation were evaluated. It could be shown that coupled spraying with stirring provided the fastest hydrate formation and highest gas uptakes in the hydrate phase. In the second step, extensive experimental series were executed, using various different gas compositions on the example of synthetic natural gas mixtures containing methane, ethane and propane. Methane is eliminated from the gas phase and stored in gas hydrates. The experiments were conducted under moderate conditions (8 bar(g), 9–14 °C), using tetrahydrofuran as a thermodynamic promoter in a stoichiometric concentration of 5.56 mole%. High storage capacities, formation rates and separation efficiencies were achieved at moderate operation conditions supported by rough economic considerations, successfully showing the feasibility of this innovative concept. An adapted McCabe-Thiele diagram was created to approximately determine the necessary theoretical separation stage numbers for high purity gas separation requirements.

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