CN102454394A - Method for displacing methane from natural gas hydrate - Google Patents
Method for displacing methane from natural gas hydrate Download PDFInfo
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- CN102454394A CN102454394A CN2010105160475A CN201010516047A CN102454394A CN 102454394 A CN102454394 A CN 102454394A CN 2010105160475 A CN2010105160475 A CN 2010105160475A CN 201010516047 A CN201010516047 A CN 201010516047A CN 102454394 A CN102454394 A CN 102454394A
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Abstract
The invention discloses a method for displacing methane from natural gas hydrate, which comprises the following steps of: depressurizing a natural gas hydrate reservoir with underlying free gas; and injecting CO2 into the natural gas hydrate reservoir, removing mixed gas of the CO2 and natural gas, and collecting the methane. By the method, methane gas serving as clean energy can be exploited, CO2 gas which causes a greenhouse effect can be eliminated, and the occurrence probability of a geological disaster in the process of exploiting the hydrate is greatly reduced. The key point of the method is previous depressurization, so that the originally closed pore channel in sediments is dredged, and the subsequently injected CO2 gas can smoothly enter the pore channel and contact methane hydrate; therefore, the reaction area is greatly increased, and displacement efficiency is high.
Description
Technical field
The present invention relates to the exploiting ocean natural gas hydrates technical field, also belong to permafrost region exploitation of gas hydrates technical field, also belong to field of greenhouse gas treating technology, be specifically related to from the method for the mid-methane that swaps out of gas hydrates.
Background technology
Now, face of mankind two hang-ups: energy shortage and ecological deterioration.Energy shortage has been undisputable fact, and the quickening of Along with people's rhythm of life, and energy problem becomes the principal element of the development that obstructs many countries and regions.Along with the aggravation of mankind's activity, the degree that environment is destroyed is being deepened year by year, and many endangered species perhaps disappear from the earth forever, and existent environment of people also will receive unprecedented challenge.One of arch-criminal is exactly the diffusion of a large amount of greenhouse gases.
Gas hydrates (major part is a methane hydrate) are as a kind of potential clean energy resource, because of its huge reserves (be about explored organic carbon 2 times) receive widely and paying close attention to.Simultaneously, through methane, CO
2Discovering of hydrate phase balance, under same condition, CO
2Hydrate generates than methane hydrate more easily.The present invention is directed to CO
2From the principle of hydrate displace methane, a kind of new method from hydrate sediment displace methane has been proposed.
Summary of the invention
The object of the present invention is to provide a kind of method from the mid-methane that swaps out of gas hydrates.
Method provided by the invention comprises the steps: to hide to the gas hydrates that have the free gas that underlies, and carries out step-down, in said gas hydrates are hidden, injects CO then
2, get rid of CO
2With the gaseous mixture of natural gas, collect said methane.
Further, above-mentioned step-down can realize through pumping said free gas.
Before the above-mentioned step-down, the pressure that gas hydrates are hidden can be 7-10MPa, preferably 8MPa.
After the above-mentioned step-down, the pressure that gas hydrates are hidden can be 2.5-3.5MPa, preferably 3.0-3.2MPa.
Before the above-mentioned step-down and after the said step-down, the temperature that gas hydrates are hidden is 270-280K, preferably 272.7-274.7K.
Above-mentioned CO
2Injection rate can be amount greater than natural gas in the said gas hydrates; Preferred injection rate is with CO in the said gaseous mixture
2Reach more than 90% and be as the criterion.
Above-mentioned natural gas specifically can be methane; Said free gas is a methane.
Above-mentioned existence is underlied in the gas hydrates of free gas, and said free gas is 5-9mol, 6.7mol preferably, and natural gas is 1-3mol, preferably 2.15mol in the said gas hydrates; Free water during said gas hydrates are hidden is 1-3mol, preferably 2.1mol.
Further, above-mentioned CO
2Injection rate can be 3-8mol, preferably 4.57mol.
The saturation ratio of the gas hydrates during above-mentioned gas hydrates are hidden can be less than 50%, and preferably 10%.
The present invention relates to a kind of CO that utilizes gaseous state
2From the method for hydrate displace methane, the method both can have been exploited out the methane gas as clean energy resource, can eliminate the CO that brings greenhouse effect again
2Gas, in addition, the method also greatly reduces the possibility that geological disaster takes place in the production of water compound process.Specifically, it is to compose the hydrate sediment of leaving the volt free gas that the method is mainly levied right, and earlier through step-down, the discharge section free gas makes hydrate formation pressure be lower than the equilibrium pressure of the methane hydrate under this condition, and is higher than CO
2The equilibrium pressure of hydrate, purpose are the decomposition that impels methane hydrate, CO
2The generation of hydrate; Inject CO then
2Gas begins exhaust outward simultaneously to the free gas-bearing formation that underlies, guarantee the pressure stability of this system; Gas mixture (the CO that discharges
2-CH
4) through after separating, CO
2Gas can be recycled; Through collecting the gaseous sample of discharging, analyze its composition, CO in gas composition
2Concentration greater than 90% o'clock, can stop in free gas-bearing formation, annotating CO
2, close the outlet opening valve simultaneously.The key point of the method is the step-down in early stage, makes the duct mediation that was closed originally in the deposit, the CO that injected afterwards
2Gas can get into smoothly in the duct and contact with methane hydrate, has increased response area so greatly, makes displacement efficiency very high.
Description of drawings
Fig. 1 is in the embodiment of the invention, the middle mutually CH of hydrate
4, CO
2Mole fraction over time.
Fig. 2 is in the embodiment of the invention; The percentage that accounts for the methane the initial water compound from the mid-methane that swaps out of hydrate over time; This study is result of the present invention among the figure; Ota (2005) liquid CO2 is the result of contrast 1, and Zhou (2008) liquid CO2 is the result of contrast 2, and Ota (2005) Gaseous CO2 is the result of contrast 3.
Fig. 3 is in the embodiment of the invention, the replacement rate of methane over time, This study is result of the present invention among the figure, Zhou (2008) liquid CO2 is contrast 2 result.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Among the following embodiment,, be conventional method like no specified otherwise.
Embodiment 1, from the mid-methane that swaps out of gas hydrates
One, preparation methane hydrate
1, preparation porous media deposit
With sand-8 ℃ freezing 48 hours, with the Na of 3.35% (mass percentage concentration)
2SO
4The aqueous solution is freezing 48 hours at 0 ℃.When the bath temperature of temperature of reaction kettle to be controlled is stabilized in 272.7K and reaches 4 hours, with sand and salt solution (Na
2SO
4The aqueous solution) stir fast and pack in the agitated reactor, the ratio of sand and salt solution is decided according to different water saturation (moisture volume accounts for the mark of whole voids volume in the porous media hole).In the present embodiment, sand 8700g, salt solution 270g, hydrate saturation ratio (hydrate of generation accounts for the mark of whole voidage) reaches 10%.
2, preparation methane hydrate
On the basis of step 1, pour pressure 8MPa in methane gas to the agitated reactor from the agitated reactor bottom, generate the methane hydrate sample.When the pressure of agitated reactor no longer reduces in 12 hours, think that methane hydrate generates fully.
This moment the methane 2.15mol in the methane hydrate, the free methane 6.7mol in the entire reaction still, the free water in the whole hydrate sediment is 2.1mol.Temperature with water-bath is set to the needed temperature 274.7K of experiment then, and stablizes more than 12 hours.
Two, step-down, logical CO2
On the basis of step 2, from agitated reactor bottom exhaust (methane of methane hydrate below is discharged), the first step slowly reduces the interior pressure of agitated reactor to 3.5MPa, and the counterbalance valve in exit is set to (being 3.1MPa in the present embodiment) under this pressure; The pressure that the second quick step-down of step is set from 3.5MPa to counterbalance valve; Inject CO from the agitated reactor bottom then
2Gas contains methane and CO from the discharge of agitated reactor top exit
2Gaseous mixture because the rate of discharge of counterbalance valve control gaseous mixture can be kept and send out about the pressure 3.1MPa that answers in the still.The concentration of methane is lower than 10% (or CO in the mist of discharging
2Greater than 90%) time, stop to annotate CO
2Gas, and the inlet of off-response still and outlet opening.Whenever take out gaseous sample at a distance from 24 hours from the agitated reactor bottom, carry out the gas phase composition analysis.At this moment, the amount of injecting CO2 is 4.57mol, and reacting kettle inner pressure is 3.18MPa, and reactor temperature is 274.7K.
Three, collect
Get 3 gas parallel sample from the agitated reactor bottom every day, carries out the gas composition analysis, and the average of getting 3 samples is as final result.
1, the amount of methane in the statistics gaseous sample calculates the percentage that methane accounts for methane in the initial methane hydrate, the namely for methane displacement efficiency; Simultaneously, calculate the mole fraction of methane and CO2 in the hydrate, seen Fig. 1.
This experiment is provided with 3 contrasts simultaneously: contrast 1, contrast 2 and contrast 3.The result is as shown in Figure 2, and as at 12h, the methane displacement efficiency is 10.2% in this experiment, and contrast 1 is 3.7%, and contrast 2 is 3.7%, and contrast 3 is 6.8%; The methane displacement efficiency is 16% in this experiment of 36h, and contrast 1 is 11.2%, and contrast 2 is 11.2%, and contrast 3 is 10.4%; The methane displacement efficiency is 19.6% in this experiment of 60h, and contrast 1 is 15.2%, and contrast 2 is 15.7%, and contrast 3 is 12.9%; The methane displacement efficiency is 21.4% in this experiment of 84h, and contrast 1 is 17.9%, and contrast 2 is 17.9%, and contrast 3 is 13.9%.The methane displacement efficiency increased along with the time in this experiment, and was higher than contrast 1, contrast 2 and contrasts 3.
What report in the document is CO2 emulsion replacement result than liquid CO 2 good (contrast 2), and liquid CO 2 is than gas CO2 good (contrast 2).Adopt gas CO2 among the present invention, but replacement result even better than liquid CO 2.
Wherein contrast 1: list of references Ota, M.; Morohashi, K.; Abe, Y.; Watanabe, M.; Smith, R.L.and Inomata, H.Replacement of CH4 in the hydrate by use of liquid CO2.Energy conversion and management, 2005,46:1680-1691.
Contrast 2: list of references Zhou, X.T.; Fan, S.S.; Liang, D.Q.and Du, J.W.Replacement of methane from quartz sand-bearing hydrate with carbon dioxide-in-water emulsion.Energy & Fuels, 2008,22:1759-1764.
Contrast 3: list of references Ota, M.; Abe, Y.; Watanabe, M.; Smith, R.L.and Inomata, H.Methane recovery from methane hydrate using pressurized CO2.Fluid phase equilibria, 2005,228-229:553-559.
2, the replacement rate of methane has also been added up in this experiment, and is the contrast of this step with above-mentioned contrast 2.The displacement efficiency of methane defines as follows:
The result is as shown in Figure 3, in the method provided by the invention, and the replacement rate of methane, it reduces along with the prolongation of time, but replacement rate is higher than contrast 2.
Claims (8)
1. from the method for the mid-methane that swaps out of gas hydrates, comprise the steps: to hide, carry out step-down, in said gas hydrates are hidden, inject CO then to the gas hydrates that have the free gas that underlies
2, get rid of CO
2With the gaseous mixture of natural gas, collect said methane.
2. the method for claim 1 is characterized in that: said step-down realizes through pumping said free gas.
3. according to claim 1 or claim 2 method, it is characterized in that: before the said step-down, the pressure that gas hydrates are hidden is 7-10MPa, preferably 8MPa.
4. like arbitrary described method among the claim 1-3, it is characterized in that: after the said step-down, the pressure that gas hydrates are hidden is 2.5-3.5MPa, preferably 3.0-3.2MPa.
5. like arbitrary described method among the claim 1-4, it is characterized in that: before the said step-down and after the said step-down, the temperature that gas hydrates are hidden is 270-280K, preferably 272.7-274.7K.
6. like arbitrary described method among the claim 1-5, it is characterized in that: said CO
2Injection rate with CO in the said gaseous mixture
2Reach more than 90% and be as the criterion.
7. like arbitrary described method among the claim 1-6, it is characterized in that: said natural gas is a methane; Said free gas is a methane.
8. like arbitrary described method among the claim 1-7, it is characterized in that: the saturation ratio of the gas hydrates during said gas hydrates are hidden is less than 50%, and preferably 10%.
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| CN2010105160475A CN102454394A (en) | 2010-10-15 | 2010-10-15 | Method for displacing methane from natural gas hydrate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103174407A (en) * | 2013-03-19 | 2013-06-26 | 中国石油天然气股份有限公司 | Method of using CO2 natural gas replacement emulsion to replace methane in stratum natural gas hydrate |
| CN103216219A (en) * | 2013-05-01 | 2013-07-24 | 吉林大学 | Method for extracting natural gas hydrate through CO2/N2 underground replacement |
| CN103603638A (en) * | 2013-11-13 | 2014-02-26 | 大连理工大学 | Natural gas hydrate CO2 substitution extraction method combined with depressurization |
| CN103982165A (en) * | 2014-05-21 | 2014-08-13 | 中国石油大学(北京) | Method for extracting natural gas hydrate by using gas mixture of CO2 and H2 |
| CN105422056A (en) * | 2016-01-26 | 2016-03-23 | 辽宁石油化工大学 | Method for mining natural gas hydrate in deep seafloor through carbon dioxide method |
| CN106351615A (en) * | 2016-10-31 | 2017-01-25 | 重庆大学 | Hydrate production method assisted by reaction of haloid acid liquor and soluble carbonate |
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| US20040200618A1 (en) * | 2002-12-04 | 2004-10-14 | Piekenbrock Eugene J. | Method of sequestering carbon dioxide while producing natural gas |
| US20050121200A1 (en) * | 2003-12-04 | 2005-06-09 | Alwarappa Sivaraman | Process to sequester CO2 in natural gas hydrate fields and simultaneously recover methane |
| CN101052780A (en) * | 2004-09-23 | 2007-10-10 | 科诺科菲利浦公司 | Production of free gas by gas hydrate conversion |
| CN101761326A (en) * | 2009-12-30 | 2010-06-30 | 中国科学院广州能源研究所 | Simulation method and experimental device for carbon dioxide replacement exploitation of gas hydrate |
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2010
- 2010-10-15 CN CN2010105160475A patent/CN102454394A/en active Pending
Patent Citations (4)
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| US20040200618A1 (en) * | 2002-12-04 | 2004-10-14 | Piekenbrock Eugene J. | Method of sequestering carbon dioxide while producing natural gas |
| US20050121200A1 (en) * | 2003-12-04 | 2005-06-09 | Alwarappa Sivaraman | Process to sequester CO2 in natural gas hydrate fields and simultaneously recover methane |
| CN101052780A (en) * | 2004-09-23 | 2007-10-10 | 科诺科菲利浦公司 | Production of free gas by gas hydrate conversion |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103174407A (en) * | 2013-03-19 | 2013-06-26 | 中国石油天然气股份有限公司 | Method of using CO2 natural gas replacement emulsion to replace methane in stratum natural gas hydrate |
| CN103174407B (en) * | 2013-03-19 | 2015-07-08 | 中国石油天然气股份有限公司 | Method of using CO2 natural gas replacement emulsion to replace methane in stratum natural gas hydrate |
| CN103216219A (en) * | 2013-05-01 | 2013-07-24 | 吉林大学 | Method for extracting natural gas hydrate through CO2/N2 underground replacement |
| CN103216219B (en) * | 2013-05-01 | 2015-11-18 | 吉林大学 | A kind of CO 2/ N 2the method of underground replacement exploitation of gas hydrate |
| CN103603638A (en) * | 2013-11-13 | 2014-02-26 | 大连理工大学 | Natural gas hydrate CO2 substitution extraction method combined with depressurization |
| CN103603638B (en) * | 2013-11-13 | 2016-06-22 | 大连理工大学 | A kind of gas hydrates CO in conjunction with voltage drop method2Replacement exploitation method |
| CN103982165A (en) * | 2014-05-21 | 2014-08-13 | 中国石油大学(北京) | Method for extracting natural gas hydrate by using gas mixture of CO2 and H2 |
| CN103982165B (en) * | 2014-05-21 | 2016-08-24 | 中国石油大学(北京) | One utilizes CO2and H2the method of mixed gas exploitation of gas hydrate |
| CN105422056A (en) * | 2016-01-26 | 2016-03-23 | 辽宁石油化工大学 | Method for mining natural gas hydrate in deep seafloor through carbon dioxide method |
| CN106351615A (en) * | 2016-10-31 | 2017-01-25 | 重庆大学 | Hydrate production method assisted by reaction of haloid acid liquor and soluble carbonate |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC Research Institute Applicant after: China University of Petroleum (Beijing) Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Research Center Applicant before: China University of Petroleum (Beijing) |
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Application publication date: 20120516 |