AU5372900A - Natural gas hydrates and method of producing same - Google Patents
Natural gas hydrates and method of producing same Download PDFInfo
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- AU5372900A AU5372900A AU53729/00A AU5372900A AU5372900A AU 5372900 A AU5372900 A AU 5372900A AU 53729/00 A AU53729/00 A AU 53729/00A AU 5372900 A AU5372900 A AU 5372900A AU 5372900 A AU5372900 A AU 5372900A
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Description
WO 01/00755 PCT/AUOO/00719 Natural Gas Hydrate And Method For Producing Same Field Of The Invention The present invention relates to a natural gas hydrate. More particularly, the present invention relates to a natural gas hydrate with improved gas content and 5 stability characteristics and a method for producing the same. Background Art Natural gas hydrates are a stable solid comprising water and natural gas, and have been known to scientists for some years as a curiosity. More recently, natural gas hydrates became a serious concern in regard to the transportation 10 and storage of natural gas industries in cold climates, due to the tendency of hydrates to form in pipelines thereby blocking the flow the pipelines. Natural gas hydrates may be formed by the combination of water and gas at relatively moderate temperatures and pressures, with the resulting solid having the outward characteristics of ice, being either white or grey in colour and cold to 15 the touch. At ambient temperatures and pressures natural gas hydrates break down releasing natural gas. Conventionally, gas storage is achieved through re-injecting into reservoirs, or pressurised reservoirs or through the use of line pack, where the volume of the pipeline system is of the same order of magnitude as several days' customer 20 consumption. The use of natural gas hydrates in storage has the potential to provide a flexible way of storing reserves of natural gas to meet short to medium term requirements in the event of excessive demands or a reduction in the delivery of gas from source. In any application, the gas content of the hydrate and the temperature at which 25 the hydrate begins to decompose (i.e. the hydrate desolution temperature), are significant criteria that require consideration. Known natural gas hydrates exhibit WO 01/00755 PCT/AUOO/00719 -2 a gas content of 163 Sm 3 per m 3 of hydrate, and a hydrate desolution temperature, at atmospheric pressure, of -1 50C. It is one object of the present invention to provide a natural gas hydrate and a method for the production thereof, with improved gas content and hydrate 5 desolution temperature. Throughout the specification, unless the context requires otherwise, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers but not the exclusion of any other integer or group of integers. 10 Disclosure Of The Invention In accordance with the present invention there is provided a natural gas hydrate with a gas content in excess of 163 Sm 3 per M 3 . Preferably, the natural gas hydrate has a gas content in excess of 170 Sm 3 per M 3 . Preferably still, the natural gas hydrate has a gas content in excess of 180 Sm 3 per M 3 . Further and 15 still preferably, the natural gas hydrate has a gas content of 186 Sm 3 per M 3 . In a highly preferred form of the invention, the natural gas hydrate has a gas content in excess of 220 Sm 3 per M 3 . Preferably still, the natural gas hydrate has a gas content in excess of approximately 227 Sm 3 per M 3 . Preferably, the natural gas hydrate exhibits a hydrate desolution temperature in 20 excess of -150C at atmospheric pressure. Preferably still, the natural gas hydrate exhibits a hydrate desolution temperature in excess of -130C at atmospheric pressure. Further and still preferably, the natural gas hydrate exhibits a hydrate resolution temperature in excess of -11 C at atmospheric pressure. In a highly preferred form of the invention, the natural gas hydrate exhibits a hydrate 25 desolution temperature in excess of -50C at atmospheric pressure. Preferably still, the natural gas hydrate exhibits a hydrate resolution temperature in excess of 3C at atmospheric pressure.
WO 01/00755 PCT/AUOO/00719 -3 In accordance with the present invention, there is further provided a natural gas hydrate which exhibits a hydrate desolution temperature in excess of -150C at atmospheric pressure. Preferably, the natural gas hydrate exhibits a hydrate desolution temperature in excess of -130C at atmospheric pressure. Preferably 5 still, the natural gas hydrate exhibits a hydrate resolution temperature in excess of -11 0 C at atmospheric pressure. Further and still preferably, the natural gas hydrate exhibits a hydrate resolution temperature in excess of -5'C at atmospheric pressure. In a highly preferred form of the invention, the natural gas hydrate exhibits a hydrate desolution temperature in excess of 30C at atmospheric 10 pressure. Preferably, the natural gas hydrate has a gas content in excess of 163 Sm 3 per m 3 . Preferably still, the natural gas hydrate has a gas content in excess of 170 Sm 3 per M 3 . Further and still preferably, the natural gas hydrate has a gas content in excess of 180 Sm 3 per m3. In a highly preferred form of the invention, 15 the natural gas hydrate has a gas content of 186 Sm 3 per M 3 . In one form of the invention, the natural gas hydrate has a gas content in excess of 220 Sm 3 per M 3 . Preferably still, the natural gas hydrate has a gas content in excess of approximately 227 Sm 3 per M 3 . In accordance with the present invention there is still further provided a method for 20 the production of the natural gas hydrate of the present invention, the method comprising the steps of: combining natural gas and water to form a natural-gas water system and an agent adapted to reduce the natural gas-water interfacial tension to form a natural-gas water-agent system; 25 allowing the natural gas-water-agent system to reach equilibrium at elevated pressure and ambient temperature; and reducing the temperature of the natural gas-water-agent system to initiate the formation of the natural gas hydrate.
WO 01/00755 PCT/AUOO/00719 -4 Preferably, the method of the present invention comprises the additional step of, before combining the natural gas and water, atomising the natural gas and water. Preferably, the natural gas-water-agent system is agitated before the temperature is reduced. 5 Preferably, the agent is a compound that is at least partially soluble in water. In one form of the invention, the agent is an alkali metal alkylsulfonate. Preferably, where the agent is an alkali metal alkylsulfonate, the alkali metal alkylsulfonate is a sodium alkylsulfonate. Where the agent is a sodium alkylsulfonate, the agent may be selected from the group; sodium lauryl sulfate, 10 sodium 1-propanesulfonate, sodium 1-butane sulfonate, sodium 1 pentanesulfonate, sodium 1-hexane sulfonate sodium 1-heptane sulfonate, sodium 1 -octanesulfonate, sodium 1 -nonanesulfonate, sodium 1 -decanesulfonate, sodium 1-undecanesulfonate, sodium 1-dodecanesulfonate and sodium 1 tridecane sulfonate. 15 Where the agent is an alkali metal sulfonate, the amount of agent added is preferably such that the concentration of the agent in the natural gas-water-agent system is less than about 1 % by weight. Preferably still, the amount of agent added results in a concentration of the agent less than about 0.5% by weight. Further and still preferably, the amount of agent added results in a concentration 20 of the agent between about 0.1 and 0.2% by weight. In an alternate form of the invention, the agent is sodium lauryl sulfate. Where the agent is sodium lauryl sulfate, the amount of agent added is preferably such that the concentration of the agent in the natural gas-water-agent system is less than about 1% by weight. Preferably still, the amount of agent added results in a 25 concentration of the agent less than about 0.5% by weight. Further and still preferably, the amount of agent added results in a concentration of the agent between about 0.1 and 0.2% by weight.
WO 01/00755 PCT/AUOO/00719 In an alternate form of the invention, the agent is sodium tripolyphoshate. Where the agent is sodium tripolyphosphate, the amount of agent added is preferably such that the concentration of the agent in the natural gas-water-agent system is between about 1 and 3 % by weight. 5 In an alternate form of the invention, the agent is an alcohol. Preferably, where the agent is an alcohol, the agent is isopropyl alcohol. Where the agent is isopropyl alcohol, the amount of agent added is preferably such that the concentration of the agent in the natural gas-water-agent system is about 0.1 % by volume. 10 The degree to which the temperature is decreased depends upon the degree to which the pressure is elevated. However, preferably the pressure exceeds about 50 bars and preferably, the temperature is below about 180C. Preferably, the natural-gas-water-agent system is constantly mixed throughout the hydration process. 15 Examples The present invention will now be described in relation to five examples. However, it must be appreciated that the following description of those examples is not to limit the generality of the above description of the invention. Hydrate Formation 20 Example 1 - isopropyl alcohol Water and isopropyl alcohol (0.1% by volume) were introduced into a sapphire cell. The cell was pressurised with methane gas above the hydrate equilibrium pressure for a normal water-methane system. Equilibrium was achieved quickly by bubbling the methane through the water phase. The system was stabilised at 25 a pressure of 206 bars (3000psia) and room temperature of 230C.
WO 01/00755 PCT/AUOO/00719 -6 The temperature was then reduced at a rate of 0.10C per minute using a thermostat air bath to 17.70C. Crystals of methane hydrate were observed on the sapphire window, and hydrate formation was assumed to be complete when pressure had stabilised in the cell. 5 Example 2 - isopropyl alcohol Water and isopropyl alcohol (0.1% by volume) were introduced into a sapphire cell. The cell was pressurised with methane gas above the hydrate equilibrium pressure for a normal water-methane system. Equilibrium was achieved quickly by bubbling the methane through the water phase. The system was stabilised at 10 a pressure of 138 bars (2000psia) and room temperature of 230C. The temperature was then reduced at a rate of 0.10C per minute using a thermostat air bath to 15.50C. Crystals of methane hydrate were observed on the sapphire window, and hydrate formation was assumed to be complete when pressure had stabilised in the cell. 15 Example 3 - isopropyl alcohol Water and isopropyl alcohol (0.1% by volume) were introduced into a sapphire cell. The cell was pressurised with methane gas above the hydrate equilibrium pressure for a normal water-methane system. Equilibrium was achieved quickly by bubbling the methane through the water phase. The system was stabilised at 20 a pressure of 102 bars and room temperature of 230C. The temperature was then reduced at a rate of 0.10C per minute using a thermostat air bath to 13.1 C. Crystals of methane hydrate were observed on the sapphire window, and hydrate formation was assumed to be complete when pressure had stabilised in the cell.
WO 01/00755 PCT/AUOO/00719 -7 Example 4 - isopropyl alcohol Water and isopropyl alcohol (0.1% by volume) were introduced into a sapphire cell. The cell was pressurised with methane gas above the hydrate equilibrium pressure for a normal water-methane system. Equilibrium was achieved quickly 5 by bubbling the methane through the water phase. The system was stabilised at a pressure of 54.5 bars (800psia) and room temperature of 230C. The temperature was then reduced at a rate of 0.10C per minute using a thermostat air bath to 8.1 0C. Crystals of methane hydrate were observed on the sapphire window, and hydrate formation was assumed to be complete when 10 pressure had stabilised in the cell. Example 5 - sodium tripolyphosphate Water and sodium tripolyphosphate (1% by weight) and methane gas were introduced into a sapphire cell. The pressure was adjusted to 1400 psia, and the mixture cooled rapidly to -50C, where formation of the hydrate was observed. The 15 methane bubbling through the gas served to agitate the system. Example 6 - sodium lauryl sulfate Water and sodium lauryl sulfate (0.11% by weight) and methane gas were introduced into a sapphire cell. The mixture was pressurised to 2200psia at 300C, and left to equilibrate for 45 minutes. The mixture was then flashed into a 20 cryogenic PVT cell at -30C, causing the fluid to atomise and resulting in the formation of hydrate. Example 7 - sodium 1 -octanesulfonate Water and sodium -octanesulfonate (0.15% by weight) and methane gas were introduced into a sapphire cell. The mixture was pressurised to 2200psia at 300C, 25 and left to equilibrate for 45 minutes. The mixture was then flashed into a WO 01/00755 PCT/AUOO/00719 -8 cryogenic PVT cell at -30C, causing the fluid to atomise and resulting in the formation of hydrate. Example 8 - sodium 1 -octanesulfonate Water and sodium 1-octanesulfonate (0.1% by weight) and methane gas were 5 introduced into a sapphire cell. The mixture was pressurised to 2200psia at 300C, and left to equilibrate for 45 minutes. The mixture was then flashed into a cryogenic PVT cell at -30C, causing the fluid to atomise and resulting in the formation of hydrate. Testing desolution temperature and natural gas content of hydrate 10 Example 1 Having formed the hydrate as outlined in Example 1, excess methane was removed and the temperature of the system was reduced to -15*C, at a rate of 0.10C per minute, and the pressure of the system was observed to diminish to zero. 15 The hydrate was stored for more than 12 hours at -150C, showing no observable changes in appearance. The pressure remained at zero throughout. After 12 hours, the temperature of the system was gradually increased at a rate of 0.20C per minute, in an attempt to reverse the hydrate formation process. Throughout this stage the pressure of the system was carefully monitored and 20 recorded by way of high precision digital pressure gauges. The pressure of the system remained stable until the temperature reached -11.50C, at which point some increase was noted. The pressure continued to increase as the temperature increased until the pressure of the system stabilised at 206.3 bars at the ambient temperature of 230C.
WO 01/00755 PCT/AUOO/00719 -9 Quantities of methane and water generated from the desolution of the hydrate were measured, and the methane content of the methane hydrate was calculated to be 186 Sm 3 per M 3 . Example 5 5 Having formed the hydrate as outlined in Example 5, the system was heated carefully. The hydrate was observed to melt at approximately 20C. Based on the pressure-volume relationship, and excess methane before and after hydrate formation, the amount of methane contained in the hydrate was estimated to be in excess of 230 Sm 3 per m 3 of hydrate. 10 Examples 6 to 8 Having formed the hydrates as outlined in Examples 6 to 8, the systems were heated carefully. Each of the hydrates was observed to melt at approximately 30C. Based on the pressure-volume relationship, and excess methane before and after hydrate formation, the amount of methane contained in the hydrate produced 15 in Example 6 was estimated to be in excess of 227 Sm 3 per m 3 of hydrate. Similarly, the amount of methane contained in the hydrate produced in Example 7 was estimated to be in excess of 212 Sm 3 per m 3 of hydrate. The amount of methane contained in the hydrate produced in Example 8 was estimated to be in excess of 209 Sm 3 per m 3 of hydrate. 20 Each unique mixture of hydrocarbon and water has its own hydrate formation curve, describing the temperatures and pressures at which the hydrate will form, and it is envisaged that additional analysis will reveal optimum pressure and temperature combinations, having regard to minimising the energy requirements for compression and cooling. 25
Claims (36)
1. A natural gas hydrate characterised by a gas content in excess of 163 Sm 3 per m 3 .
2. A natural gas hydrate according to claim 1 characterised by a gas content in 5 excess of 170 Sm 3 per M 3 .
3. A natural gas hydrate according to claim 1 characterised by a gas content in excess of 180 Sm 3 per M 3 .
4. A natural gas hydrate according to claim 1 characterised by a gas content in excess of 186 Sm 3 per M 3 . 10
5. A natural gas hydrate according to claim 1 characterised by a gas content in excess of 220 Sm 3 per M 3 .
6. A natural gas hydrate according to claim 1 characterised by a gas content in excess of approximately 227 Sm 3 per M 3 .
7. A natural gas hydrate according to any one of claims 1 to 6 characterised by a 15 hydrate resolution temperature in excess of -15OC at atmospheric pressure.
8. A natural gas hydrate according to claim 7 characterised by a hydrate resolution temperature in excess of -130C at atmospheric pressure.
9. A natural gas hydrate according to claim 7 characterised by a hydrate resolution temperature in excess of -11 OC at atmospheric pressure. 20
10. A natural gas hydrate according to claim 7 characterised by a hydrate resolution temperature in excess of -5*C at atmospheric pressure.
11. A natural gas hydrate according to claim 7 characterised by a hydrate resolution temperature in excess of -30C at atmospheric pressure. WO 01/00755 PCT/AUOO/00719 - 11
12. A natural gas hydrate according to claim 7 characterised by a hydrate resolution temperature in excess of 30C at atmospheric pressure.
13. A method for the production of the natural gas hydrate of any one of claims 1 to 12 characterised by the steps of: 5 combining natural gas and water to form a natural-gas water system and an agent adapted to reduce the natural gas-water interfacial tension to form a natural-gas water-agent system; allowing the natural gas-water-agent system to reach equilibrium at elevated pressure and ambient temperature; and 10 reducing the temperature of the natural gas-water-agent system to initiate the formation of the natural gas hydrate.
14. A method of according to claim 13 characterised by the additional step of, before combining the natural gas and water, atomising the natural gas and water.
15 15. A method according to claim 13 or claim 14 characterised by the natural gas water-agent system being agitated before the temperature is reduced.
16. A method according to any one of claims 13 to 15 characterised in that the agent is a compound that is at least partially soluble in water.
17. A method according claim 16 characterised in that the agent is an alkali metal 20 alkylsulfonate.
18. A method according to claim 17 characterised in that the alkali metal alkylsulfonate is a sodium alkylsulfonate.
19. A method according to claim 18 characterised in that the agent is selected from the group; sodium lauryl sulfate, sodium 1-propanesulfonate, sodium 1 25 butane sulfonate, sodium 1 -pentanesulfonate, sodium 1 -hexane sulfonate WO 01/00755 PCT/AUOO/00719 -12 sodium 1-heptane sulfonate, sodium 1-octanesulfonate, sodium 1 nonanesulfonate, sodium 1 -decanesulfonate, sodium 1 -undecanesulfonate, sodium 1 -dodecanesulfonate and sodium 1 -tridecane sulfonate.
20. A method according to any one of claims 17 to 19 characterised in that the 5 amount of agent added is such that the concentration of the agent in the natural gas-water-agent system is less than about 1 % by weight.
21. A method according to claim 20 characterised in that the amount of agent added results in a concentration of the agent less than about 0.5% by weight.
22. A method according to claim 21 characterised in that the amount of agent 10 added results in a concentration of the agent between about 0.1 and 0.2% by weight.
23. A method according to claim 16 characterised in that the agent is sodium lauryl sulfate.
24. A method according to claim 23 characterised in that the amount of agent 15 added is preferably such that the concentration of the agent in the natural gas water-agent system is less than about 1 % by weight.
25. A method according to claim 24 characterised in that the amount of agent added results in a concentration of the agent less than about 0.5% by weight.
26. A method according to claim 25 characterised in that the amount of agent 20 added results in a concentration of the agent between about 0.1 and 0.2% by weight.
27. A method according to claim 16 characterised in that the agent is sodium tripolyphoshate.
28. A method according to claim 27 characterised in that the amount of agent 25 added is preferably such that the concentration of the agent in the natural gas water-agent system is between about 1 and 3 % by weight. WO 01/00755 PCT/AUOO/00719 - 13
29. A method according to claim 16 characterised in that the agent is an alcohol.
30. A method according to claim 29 characterised in that the agent is isopropyl alcohol.
31. A method according to either claim 29 or 30 characterised in that the amount 5 of agent added is preferably such that the concentration of the agent in the natural gas-water-agent system is about 0.1 % by volume.
32. A method according to any one of claims 13 to 31 characterised in that the pressure exceeds about 50 bars.
33. A method according to any one of claims 13 to 32 characterised in that the 10 temperature is below about 180C.
34. A method according to any one of the preceding claims wherein the natural gas-water-agent system is constantly mixed throughout the method.
35. A method for the production of the natural gas hydrate substantially described herein with reference to any one of Examples 1 to 8. 15
36. A natural gas hydrate substantially as herein described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU53729/00A AU778742B2 (en) | 1999-06-24 | 2000-06-23 | Natural gas hydrates and method of producing same |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPQ1188A AUPQ118899A0 (en) | 1999-06-24 | 1999-06-24 | Natural gas hydrate and method for producing same |
| AUPQ1188 | 1999-06-24 | ||
| AU53729/00A AU778742B2 (en) | 1999-06-24 | 2000-06-23 | Natural gas hydrates and method of producing same |
| PCT/AU2000/000719 WO2001000755A1 (en) | 1999-06-24 | 2000-06-23 | Natural gas hydrate and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU5372900A true AU5372900A (en) | 2001-01-31 |
| AU778742B2 AU778742B2 (en) | 2004-12-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU53729/00A Expired AU778742B2 (en) | 1999-06-24 | 2000-06-23 | Natural gas hydrates and method of producing same |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU778742B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO172080C (en) * | 1990-01-29 | 1993-06-02 | Gudmundsson Jon Steinar | PROCEDURE FOR THE PREPARATION OF GAS HYDRATES AND APPLIANCES FOR PERFORMING THE SAME |
| US5536893A (en) * | 1994-01-07 | 1996-07-16 | Gudmundsson; Jon S. | Method for production of gas hydrates for transportation and storage |
| GB9601030D0 (en) * | 1996-01-18 | 1996-03-20 | British Gas Plc | a method of producing gas hydrate |
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2000
- 2000-06-23 AU AU53729/00A patent/AU778742B2/en not_active Expired
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| Publication number | Publication date |
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| AU778742B2 (en) | 2004-12-16 |
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| PC1 | Assignment before grant (sect. 113) |
Owner name: METASOURCE PTY. LTD. Free format text: THE FORMER OWNER WAS: WOODSIDE ENERGY LIMITED |
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| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |