Natural Gas Hydrates: Separation and Gas Content

Børge Nerland
December 1995

Summary

Gas hydrates made of a simulated natural gas mixture, consisting of methane, ethane and propane, and water has been produced and studied in regard to different properties. Properties that have been studied are gas content and separability from water. In addition the effects of gas solubility and some additives on the rate of formation have been looked at. The work has been carried out with a simple laboratory rig at the Norwegian Institute of Technology. The purpose of the experiments has been to obtain as large gas content as possible by means of gravity separation of the hydrate/water slurry through different filters. Separation of the two phases seems to be very difficult using the gravitational force only. A gas content between 120 and 130 Sm$^3$ gas per m$^3$ hydrate has been obtained in several experiments, and 150 Sm$^3$ gas per m$^3$ hydrate was obtained as a maximum in this study. The rate of gas consumption seems to improve greatly when putting additives, silver iodide and bentonite, to the hydrate formation.

Introduction

The world's demand for natural gas is increasing~\cite{comm}. This fact is also supported by another demand for better technical solutions and more cost effective developments in the gas industry to be competitive in the future ~\cite{mellby}. A new concept for storage and large scale transportation of natural gas as frozen hydrate has been proposed. This is called the Gas-in-Ice concept~\cite{gud1} and is thought of as a future competitor with the conventional LNG (Liquified Natural Gas) technology~\cite{hylng}. The idea is primarily based on the fact that if the gas hydrates are stored adiabatically, they will remain stable outside the conventional equilibrium area, that is at atmospheric pressure and temperature above the equilibrium temperature. This means that no pressurized tanks are needed for storage or transport purpose, that makes the concept a promising and competitive potential for cost effective development of gas delivery.

The Gas-In-Ice concept has been patented by Professor Gudmundsson at the Norwegian Institute of Technology (NTH) in cooperation with Aker Engineering. An early stage evaluation was done by Hveding in 1994~\cite{frode}. The concept is now undergoing a more detailed study than earlier, and some rough engineering work and cost estimates have been done~\cite{aker}. In addition a project group of several possible future participants is being formed. The idea is to obtain fundings for building a pilot plant so the main assumptions of the concept can be verified on a larger scale as a basis for a future industrial process.

Gas hydrates have throughout the development of the petroleum industry almost without exceptions been seen as a problem due to plugging of pipelines and process equipment. Due to this, most of the work done on gas hydrates has focused on hydrate prevention and inhibition~\cite{katz}. However, recent work done on the Gas-in-Ice concept has considered hydrates from the other side and tried to obtain knowledge from a "positive" point of view using both experience from earlier work and new knowledge. The experimental work done at NTH has been implemented with simple but convenient laboratory equipment.

The overall purpose of the Gas-in-Ice concept is to store/transport gas as efficiently and cost effective as possible. This is dependent upon several parameters, but the main ones affecting the hydrate process are said to be rate of formation, gas content and the stability of hydrates. The work done at NTH has focused on these parameters, but the work is far from completely answering all the questions asked.

The main challenge of this study is to produce gas hydrates with as high gas content as possible. This will include an experimental phase for separating hydrate from liquid water and also to look at the methods used in the industry for separating solid-liquid slurries. The effect of some additives on separation efficiency and rate of formation will also be investigated.

Conclusions

The rate of formation for gas hydrates seem to be dependent on the amounts of air dissolved in the aqueous hase.

The rate of formation can be affected by additives, molecular or solid, as shown in this experimental work.

Separation of hydrate/water slurry by settling is very difficult. The separation was not improved using different filters.

The potential for storing large amounts of gas in hydrates have been proven, even though sufficient separation was not obtained.

References

\bibitem{comm}Chommichau, A. (1994) {\it What is the Cost of Supply}, Offshore Northern Seas, Stavanger, 11pp.

\bibitem{mellby}Mellbye, P. and Tungland, K.(1994) {\it Norwegian Natural Gas Supplied to Europe}, GASTECH 94, Session 9, Paper 4, Kuala Lumpur, 22 pp.

\bibitem{gud1}Gudmundsson, J.S. and Parlaktuna, M. (1991) {\it GAS-IN-ICE: Concept Evaluation}, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, Technical Report, 110 pp.

\bibitem{hylng}Gudmundsson, J.S., B{\o}rrehaug, A. and Hveding, F. (1995) {\it Frozen Hydrate Compared to LG}, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, Technical Report, 29 pp.

\bibitem{frode}Hveding, F. (1994) {\it The Hydrate Chain Compared to the LNG Chain}, Diploma Thesis, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, 87 pp.

\bibitem{aker}Aker Engineering A/S (1995) {\it Natural Gas Hydrates for Large Scale, Long Distance Gas Transportation - A Feasibility Study}, Internal Report in the NGH Project Group, Oslo, November 1995, 80 pp.

\bibitem{katz}Katz, D.L.(1959) {\it Handbook of Natural Gas Engineering}, McGraw-Hill Series in Chemical Engineering, McGraw-Hill, New York, 802 pp.

\bibitem{dillon}Dillon, W. (1992) {\it Gas Hydrates -- A New Frontier}, U.S. Geological Survey, Marine and Coastal Program, Internet site http://www.usgs.gov/.

\bibitem{kuustra}Kuustraa, V.A. and Hammershaimb, E.C.(1983) {\it Handbook of Gas Hydrate Properties and Occurence}, No. DE-AC21-(82Mc19239), Lewin and Associates Inc.

\bibitem{sloan}Sloan, E.D.(1990) {\it Clathrate Hydrates of Natural Gases}, Marcel Dekker, Inc., New York, 641 pp.

\bibitem{aftabvol}Khokar, A.A.(1994) {\it Volume Properties of Hydrates}, in GAS-IN-ICE: Hydrate Formation, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, 20 pp.

\bibitem{makogon}Makogon, J.F.(1981) {\it Hydrates of Natural Gas}, PennWell Publishing Company, Tulsa, 237 pp.

\bibitem{handa}Handa, Y.P.{\it A Calorimetric Study of Naturally Occuring Gas Hydrate}, Ind. Eng. Chem. Res. 27, 872-874.

\bibitem{mccain}McCain, W.D.(1981) {\it The Properties of Petroleum Fluids}, 2nd ed., PennWell Publishing Company, Tulsa, 474-489.

\bibitem{blaa}Gudmundsson, J.S.(1994) {\it GAS-IN-ICE: Hydrate Formation}, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, Technical Report, 80 pp.

\bibitem{uhlig}Uhlig, H.H.(1937) {\it The Solubilities of Gases and Surface Tension}, Journal of Physical Chemistry, vol.41, No.9, p.1215-1225.

\bibitem{berner}Berner, D.(1992) {\it The Marine Transport Of Natural Gas in Hydrate Form}, Proceedings, Second International Offshore and Polar Engineering Conference, San Francisco, USA, June 14-19, 1992, Vol. I, 636-643.

\bibitem{akersept}Aker Engineering A/S (1995) {\it Natural Gas Hydrates for Large Scale, Long Distance Gas Transportation - A Feasibility Study}, Internal Report in the NGH Project Group, First Proposal, Oslo, September 1995, 80 pp.

\bibitem{gudspe}Gudmundsson, J.S., Parlaktuna, M. and Khokar, A.A.(1994) {\it Storage of Natural Gas as Frozen Hydrate}, SPE Production Engineering, February, 69-73.

\bibitem{ershov}Ershov, E.D and Yakushev, V.S. (1992) {\it Experimental Research on Gas Hydrate Decomposition in Frozen Rocks}, Cold Regions Science and Technology, 20, Elsevier Science Publishers B.V, Amsterdam, 147-156.

\bibitem{form}Gudmundsson, J.S. and Parlaktuna, M. (1995) {\it GAS-IN-ICE: Formation Rate and Gas Content}, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, Technical Report, 53 pp.

\bibitem{gashild}Ulfsnes, G.{\AA}.(1995) {\it Separasjon av Hydrater og Vann/Kondensat}, Project Work, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, 20 pp.

\bibitem{perry}Perry, R.H. and Green, D.(1984) {\it Perry's Chemical Engineers' Handbook}, 6th ed., McGraw-Hill, New York, 19-1 - 19-109.

\bibitem{sep}Schweitzer, P.A.(1979) {\it Handbook of Separation Techniques for Chemical Engineers}, McGraw-Hill, New York, 4-36 - 4-54.

\bibitem{thomas}L{\aa}hne, T. (1995) {\it Natural Gas Hydrates - A Simulation Study}, Diploma Thesis, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, in preparation.

\bibitem{gasprog}Gudmundsson, J.S. and Parlaktuna, M. (1995) {\it Physical Properties of Natural Gases - Computer Program and Subroutines}, Department of Petroleum Engineering and Applied Geophysics, Norwegian Institute of Technology, University of Trondheim, Technical Report.


Last modified: Fri Jan 12 16:55:44 NFT 1996