CN1959179A - Method for forming hydrate of natural gas in active carbon - Google Patents
Method for forming hydrate of natural gas in active carbon Download PDFInfo
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- CN1959179A CN1959179A CN 200610150853 CN200610150853A CN1959179A CN 1959179 A CN1959179 A CN 1959179A CN 200610150853 CN200610150853 CN 200610150853 CN 200610150853 A CN200610150853 A CN 200610150853A CN 1959179 A CN1959179 A CN 1959179A
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Abstract
A method for forming natural gas hydrate in activated carbon includes adding activated carbon and distilled water in pressure tank, setting mass ratio of distilled water to activated carbon to be 0.8-2.1: 1 and pressure of pressure tank to be 3-10Mpa as well as temperature in pressure tank to be -5-25deg.c, filling natural gas into said tank then forming natural gas hydrate after 30-200 minutes reaction.
Description
Technical field
The present invention relates to a kind of formation method of gas hydrates.
Background technique
Absorption natural gas-storing (ANG) technology is abroad to begin one's study from the nineties, and becomes a kind of new rock gas storing technology that is used for gas-fueled vehicles.The key problem of absorption natural gas-storing technology has two: the one, and the preparation of high performance super-activated carbon; The 2nd, effective solution of heat of adsorption effect.Along with the raising of process for preparing activated carbon, first core technology problem solves substantially; Can and whether second core technology problem solves amount and the adsorption desorption speed that is directly connected to the absorption natural gas-storing, also determining absorption natural gas-storing technology use on a large scale simultaneously.
At present, the ANG technology is in laboratory stage always, it is shorter that the key issue that restriction ANG technology is applied on automobile is that automobile is once inflated operating range, and this mainly is because (being that the heat that produces in the adsorptive process can not shift out fast and effectively) that the thermal effect of sorbent adsorption desorption rock gas causes.
Along with gas hydrates are found in the whole world on a large scale, the formation mechanism of research gas hydrates in porous medium has great importance for exploitation of gas hydrate.Because the gas hydrates decomposition rate is slow, use comparatively safe reliable, the gas hydrates accumulating is compared not only safe and reliable but also economical and practical with liquefaction accumulating, compressing, stalling and transporting and oil pipeline and storage, so it can be used as the effective means of a kind of storage and transport natural gas.
At present, the artificial synthesis method of gas hydrate mainly contains two kinds of forms: the one, the rock gas feeding is filled in the container of water, and under certain pressure and temperature, stir the formation gas hydrates; The 2nd, in water, add surface active agent (as lauryl sodium sulfate or neopelex), reduce the surface tension of water by surface active agent, increase effective contact of natural G﹠W, thereby promote the quick formation of gas hydrates.Employing method one exists the speed that forms gas hydrates slow, and has consumed lot of energy by artificial stirring or machine stirring, simultaneously, is mixed with a lot of pure water in the hydrate of formation, is difficult to water is separated with gas hydrates; Adopt method two, surface active agent can only promote the surface of water to produce gas hydrates, the water of inside is not had promoting effect, and the price of surface active agent is more expensive.
Summary of the invention
The purpose of this invention is to provide the formation method of a kind of gas hydrates in active carbon, it can solve adopts the adsorbents adsorb natural gas-storing to exist thermal effect and employing feeding rock gas absorption natural gas-storing in water container to exist water and gas hydrates to be difficult to separate and adopt the problem that adding SURFACTANT ADSORPTION natural gas-storing exists gas hydrates to produce on the surface of water in water.
The present invention finishes like this: add active carbon and distilled water in the pressure vessel of withstand voltage 20Mpa, the mass ratio of distilled water and active carbon is 0.8～2.2: 1, pressure in the pressure vessel is 3～10Mpa, temperature in the pressure vessel is-5～25 ℃, in pressure vessel, charge into rock gas then and form gas hydrates, methane purity in the rock gas is greater than 99%, and the reaction time is 30～200min.
The present invention has following beneficial effect: one, the present invention will combine with the adsorbents adsorb natural gas-storing with the gas hydrates natural gas-storing, in being housed, the pressure vessel of active carbon adds distilled water, allow distilled water and active carbon mix, under certain temperature and pressure, feed rock gas then, make rock gas be adsorbed on the active carbon on the one hand, on the other hand, rock gas and distilled water form hydrate, promote the storage volume of rock gas greatly.The benefit of doing like this have following some: 1, increased the thermal conductivity of the active carbon in the pressure vessel, heat can be passed in time, thereby improved the extent of adsorption of active carbon; 2, because active carbon is a porous medium, distilled water is distributed in each space of active carbon, can increase the area of contact of rock gas and distilled water so greatly, promote distilled water and rock gas to form gas hydrates, thereby the boost pressure storage tank is to the storage volume of gas, and the amount that increases is considerable.In the rock gas desorption process, gas hydrates decompose, and emit rock gas; 3, in the process of active carbon adsorption rock gas, the high-carbon hydrocarbon is easier to be adsorbed onto on the active carbon and very difficult desorption, therefore influence the recycling and the working life of active carbon, in the adsorption operations process of routine, generally will remove the high-carbon hydrocarbon in the rock gas in advance.Because high-carbon hydrocarbon easier formation hydrate in the adsorptive pressure scope, therefore, add an amount of distilled water after, pre-adsorbent bed can be set remove the high-carbon hydrocarbon.Two, the present invention has that method is simple, the rock gas of operation easily, rock gas storage rate height, adsorption desorption can be used as the advantage of automotive fuel.
Embodiment
Embodiment one: the formation method of the gas hydrates of present embodiment in active carbon finished like this: add active carbon and distilled water in the pressure vessel of withstand voltage 20Mpa, the mass ratio of distilled water and active carbon is 0.8～2.2: 1, pressure in the pressure vessel is 3～10Mpa, temperature in the pressure vessel is-5～25 ℃, in pressure vessel, charge into rock gas then and form gas hydrates, methane purity in the rock gas is greater than 99%, reaction time is 30～200min, employed active carbon is in bulk, granular, need not molding bonded.
Thermometry is that the pt100 platinum resistor measures temperature in the present embodiment, thermometric error ± 0.1 ℃; Pressure measurement adopts precision pressure gauge to measure, and pressure measurement errors is ± 0.025Mpa; Pressure vessel requires to have good air-tightness.
Embodiment two: the aperture value of the active carbon in the present embodiment is 4～10nm.The aperture value of active carbon is not the smaller the better, and the aperture optimum value of active carbon is 4～10nm, and its reason is that the aperture value of active carbon is little, helps forming absorption, but after adding distilled water, stops up aperture easily; And for big slightly aperture, on the one hand can be absorbed natural gas, add distilled water on the other hand after, because the capillary condensation effect, the rock gas of absorption will be more in the space.Other method step is identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment two is: the aperture value of the active carbon of present embodiment is 7nm, neither stops up aperture, also adsorbable more rock gas.
Embodiment four: but present embodiment maximum natural gas-storing 210L in 1L distilled water, can improve storage volume greatly (feeds rock gas and forms hydrate in the distilled water that does not add active carbon, even under condition of stirring, 1L distilled water at most can natural gas-storing 40L).Other method step is identical with embodiment one.
Embodiment five: when present embodiment is 1L when the two volume sum of distilled water and active carbon, maximum adsorbable rock gas 140L.Add the storage volume that distilled water can increase rock gas as can be seen in active carbon, this accumulating for rock gas has important meaning.Other method step is identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: adding the interior distilled water of pressure vessel and the mass ratio of active carbon in the present embodiment is 1: 1, pressure in the pressure vessel is 4Mpa, temperature in the pressure vessel is 4 ℃, reaction time is 35min, adopt above-mentioned technical parameter, have and store effect preferably.
Embodiment seven: the difference of present embodiment and embodiment one is: adding the interior distilled water of pressure vessel and the mass ratio of active carbon in the present embodiment is 1.5: 1, pressure in the pressure vessel is 6Mpa, temperature in the pressure vessel is 5 ℃, and the reaction time is 120min.Adopt above-mentioned technical parameter, have preferable storage effect.
Embodiment eight: the difference of present embodiment and embodiment one is: adding the interior distilled water of pressure vessel and the mass ratio of active carbon in the present embodiment is 2: 1, pressure in the pressure vessel is 9Mpa, temperature in the pressure vessel is 5 ℃, and the reaction time is 200min.Adopt above-mentioned technical parameter, have better storage effect.
Claims (6)
1, the formation method of a kind of gas hydrates in active carbon, it is characterized in that it finishes like this: in the pressure vessel of withstand voltage 20Mpa, add active carbon and distilled water, the mass ratio of distilled water and active carbon is 0.8～2.2: 1, pressure in the pressure vessel is 3～10Mpa, temperature in the pressure vessel is-5～25 ℃, charge into rock gas then and form gas hydrates in pressure vessel, the methane purity in the rock gas is greater than 99%, and the reaction time is 30～200min.
2, the formation method of gas hydrates according to claim 1 in active carbon, the aperture value that it is characterized in that described active carbon is 4～10nm.
3, the formation method of gas hydrates according to claim 1 in active carbon, the aperture value that it is characterized in that described active carbon is 7nm.
4, the formation method of gas hydrates according to claim 1 in active carbon, it is characterized in that adding the interior distilled water of pressure vessel and the mass ratio of active carbon is 1: 1, pressure in the pressure vessel is 4Mpa, and the temperature in the pressure vessel is 4 ℃, and the reaction time is 35min.
5, the formation method of gas hydrates according to claim 1 in active carbon, it is characterized in that adding the interior distilled water of pressure vessel and the mass ratio of active carbon is 1.5: 1, pressure in the pressure vessel is 6Mpa, and the temperature in the pressure vessel is 5 ℃, and the reaction time is 120min.
6, the formation method of gas hydrates according to claim 1 in active carbon, it is characterized in that adding the interior distilled water of pressure vessel and the mass ratio of active carbon is 2: 1, pressure in the pressure vessel is 9Mpa, and the temperature in the pressure vessel is 5 ℃, and the reaction time is 200min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610150853 CN1959179A (en) | 2006-09-30 | 2006-09-30 | Method for forming hydrate of natural gas in active carbon |
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| CN 200610150853 CN1959179A (en) | 2006-09-30 | 2006-09-30 | Method for forming hydrate of natural gas in active carbon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102338278A (en) * | 2011-09-02 | 2012-02-01 | 中国石油大学(北京) | Method for increasing natural gas adsorption storage capability |
| CN105257980A (en) * | 2015-10-28 | 2016-01-20 | 重庆工商大学 | Technique method for storing methane or natural gas with low pressure |
| CN108410528A (en) * | 2018-05-30 | 2018-08-17 | 河南理工大学 | It is a kind of to be used to improve natural biomass solution of gas hydration rate and preparation method thereof |
| CN110527573A (en) * | 2019-10-09 | 2019-12-03 | 青岛科技大学 | A kind of immobilized gas hydrates continuous reaction apparatus of active carbon |
-
2006
- 2006-09-30 CN CN 200610150853 patent/CN1959179A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102338278A (en) * | 2011-09-02 | 2012-02-01 | 中国石油大学(北京) | Method for increasing natural gas adsorption storage capability |
| CN105257980A (en) * | 2015-10-28 | 2016-01-20 | 重庆工商大学 | Technique method for storing methane or natural gas with low pressure |
| CN105257980B (en) * | 2015-10-28 | 2018-04-03 | 重庆工商大学 | A kind of technical method of low pressure gas storage methane or natural gas |
| CN108410528A (en) * | 2018-05-30 | 2018-08-17 | 河南理工大学 | It is a kind of to be used to improve natural biomass solution of gas hydration rate and preparation method thereof |
| CN110527573A (en) * | 2019-10-09 | 2019-12-03 | 青岛科技大学 | A kind of immobilized gas hydrates continuous reaction apparatus of active carbon |
| CN110527573B (en) * | 2019-10-09 | 2024-03-12 | 青岛科技大学 | Active carbon immobilized natural gas hydrate continuous reaction device |
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