CN101612539A - A kind of low temperature high pressure gas hydrate replacement reaction kettle and system - Google Patents
A kind of low temperature high pressure gas hydrate replacement reaction kettle and system Download PDFInfo
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- CN101612539A CN101612539A CN200910054851A CN200910054851A CN101612539A CN 101612539 A CN101612539 A CN 101612539A CN 200910054851 A CN200910054851 A CN 200910054851A CN 200910054851 A CN200910054851 A CN 200910054851A CN 101612539 A CN101612539 A CN 101612539A
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Abstract
The present invention relates to a kind of low temperature high pressure gas hydrate replacement reaction kettle and system, the displacement reaction that is used for gas hydrate, the entire reaction still immerses in the cryogenic thermostat water-bath, keeping low temperature, vacuum system by air inlet to vacuumizing in the cryogenic high pressure reactor chamber; The gaseous component detection system is carried out gas collecting by the gas sampling mouth and is analyzed; Control pressurer system is connected with cryogenic high pressure reactor air inlet, guarantees the pressure that the cryogenic high pressure reactor needs; Data collecting system is connected with cryogenic high pressure reactor temperature-measuring port and pressure tap, the acquisition system data.Replace movable sealing with static seal, solved the problem of high pressure rotary sealing poor performance, had reliable, noiseless advantage.Can also be by the phenomenon that is taken place in the visual windows Real Time Observation reactor, and the gas component of measuring in real time in the hydrate solid by Raman spectrometer changes.
Description
Technical field
The present invention relates to a kind of gas hydrate permute field, particularly a kind of low temperature high pressure gas hydrate replacement reaction kettle.
Background technology
Human society 21 century except facing energy problem, also bearing the immense pressure of environmental protection, wherein the greenhouse effects problem is particularly outstanding.Carbon dioxide is as topmost greenhouse gases, and it is reduced discharging, captures and isolates becomes the focus that various countries pay close attention to.On February 16th, 2005, Kyoto Protocol was formally effective, indicated the implementation phase that whole world reply greenhouse gas emission beginning to move towards concrete.Utilize Hydrate Technology to handle CO
2Isothermal chamber gas has become the focus of international hydrate circle research at present, with the CO of power plant's burning and exhausting
2Gas injects the seabed, makes gas hydrate and isolate under condition of high voltage, because CO
2The density of hydrate is bigger than seawater, can permanent storage in the seabed, and this method is very little to the influence of the marine eco-environment.This technical prospect light is at all CO
2In the treatment technology, energy consumption is minimum, only is 7%.The employing Hydrate Technology is carried out purified treatment to the dusty gas of power plant emission, can successfully realize " power plant's zero-emission ".Developed countries such as Japan, the U.S. attach great importance to this Study on Technology.
On the other hand, along with the minimizing gradually of traditional energy supply, tapping a new source of energy seems more and more important.Gas hydrates are present in seabed or the tundra, land, are the solid-state cage compounds that crystallization under the high pressure low temperature condition forms by natural gas and water.Pure gas hydrates are white in color, and likeness in form ice and snow can be lighted as solid alcohol is direct, therefore, again by popular, be called " combustible ice " visually.Owing to contain a large amount of CH usually in the gas hydrates
4Or other hydrocarbon gas, therefore very easily burning, be called as " combustible ice ", the energy that burning produces is than under the equal conditions, it is all much more that coal, oil, natural gas produce, and after burning, producing any residue or discarded object hardly, damage ratio coal, oil, natural gas etc. are much smaller.Not hard to imagine, after the development technique that has solved gas hydrates, can obtain CH in the gas hydrates with cost-effective means
4, it just may replace other fossil energy that reduces day by day (as oil, coal, natural gas etc.) so, becomes a kind of main energy Source Type.
At present, the recovery method of gas hydrates mainly contains three kinds of heat shock method, decompression method and injectant methods.The maximum difficult point of exploitation is to guarantee that the shaft bottom is stable, makes CH
4Gas does not leak, does not cause greenhouse effects.At this problem, Japan has proposed " molecular Control " recovery scheme.The final of gas hydrates mineral reserve determined to pass through probing, and its difficulty is more much bigger than conventional offshore oil and gas probing, is that water is too dark on the one hand, because the decompression of gas hydrates chance can be decomposed rapidly, very easily causes blowout on the other hand.Increasing achievement shows, is changed by nature or the caused temperature and pressure of human factor, all can make decomposition of hydrate, causes environmental hazards such as submarine landslide, biological destruction and climate warming.Thereby research gas hydrates the drilling method be imminent, the research work of carrying out the decomposition of indoor and outdoor gas hydrates, synthetic method and drilling method as early as possible is very urgent, still is faced with challenge the future of gas hydrate study.This shows that " combustible ice " brings the human new hope of being not only, and new difficulty is equally also arranged, have only reasonably, the development and utilization of science that " combustible ice " just understood and real benefited for the mankind.
It is found that CO recently
2Hydrate and CH
4Hydrate structure is extremely similar, so displacement method is arisen at the historic moment.CO
2Displacement CH
4The scheme of hydrate is at first proposed by the Japanology person, the pressure condition that remains the gas hydrates stabilized zone of method foundation.Under certain temperature condition, gas hydrates keep the stable pressure ratio CO that needs
2Hydrate is higher.Therefore in a certain specific pressure limit, gas hydrates can decompose, and CO
2Hydrate then is easy to form and keeps stable.If in gas hydrates are hidden, inject CO this moment
2Gas, CO
2Gas just may generate CO with the water that gas hydrates decomposite
2Hydrate.The heat that this effect discharges can make the decomposition reaction of gas hydrates be gone on constantly.If CO
2Displacement CH
4The scheme of hydrate realizes, is two hang-ups that solved the world.
Summary of the invention
The present invention be directed to the problem of utilizing the displacement method exploitation of gas hydrate, a kind of low temperature high pressure gas hydrate replacement reaction kettle and system have been proposed, be used for gas hydrate displacement main reactor, solved the problem of high pressure rotary sealing poor performance, can also be by the phenomenon that is taken place in the visual windows Real Time Observation reactor, and the gas component of measuring in real time in the hydrate solid by Raman spectrometer changes.
Technical scheme of the present invention is: a kind of low temperature high pressure gas hydrate replacement reaction kettle, comprise reactor body, upper end cover, flange, agitating device, chassis, a pair of visual windows and several connectors, agitating device comprises motor, agitator, stirring vane, shaft, upper end cover adopts flange to be connected with kettle, between seal with teflon gasket, on the central boss of upper end cover stirring motor is installed, stirring motor adopts permanent magnet; Butt joint is equipped with agitator below the central boss of upper end cover, itself and stirring motor are in the same center line, stirring motor and agitator connect by the magnetic force coupling, and there is stirring vane the bottom of the shaft of agitator, in order to liquid in the abundant stirred tank, the chassis is arranged at the bottom at kettle, in order to fixing kettle, a pair of visual windows is arranged, the center line unanimity of two windows on the lower sides of reactor body, be looking state, several connectors are positioned at the outside of reactor.
The window material of described visual window is a quartz glass, and the sealing ring of window adopts viton seal ring, and glass window produces pressure and kettle sealing by the rotation nut.
Described stirring vane can be 2, and order is installed on the shaft, at a distance of certain distance.
Described several connectors comprise that one group is advanced leakage fluid dram, one group of porting, one group of temperature-measuring port, a pressure tap and a gas sampling mouth.Described inlet is arranged on the lateral location of flange of reactor body, and radially passes flange and enter in the reactor chamber; Leakage fluid dram is arranged in the reactor body near on the lateral location of bottom, and radially passes the still bottom, upwards vertically enters the recess in center in the reactor chamber again.Described air inlet has two, is arranged on the lateral location of flange of reactor body, and two air inlets adjoin mutually.Described gas sampling mouth is arranged in the side of upper end cover, and radially passes upper end cover and vertically enter in the reactor chamber thief hatch double as exhaust outlet again.Described temperature-measuring port has two, is arranged symmetrically in the both sides of the central boss of reactor upper end cover, and vertically passes the reactor end cap and enter in the chamber, has temperature sensor that screw thread mouth is installed on the temperature-measuring port.The double safety valve of doing of described pressure tap is arranged on the lateral location of flange of reactor body, and radially passes flange and enter in the reactor chamber.
A kind of low temperature high pressure gas hydrate exchange system, comprise low temperature high pressure gas hydrate replacement reaction kettle, also comprise air supply system, gaseous component detection system, vacuum system, cryogenic thermostat water-bath, control pressurer system, data collecting system, reactor immerses in the cryogenic thermostat water-bath, keeps the interior fluid temperature of reactor stable; Vacuum system by air inlet to vacuumizing in the cryogenic high pressure reactor chamber; The gaseous component detection system is carried out gas collecting by the gas sampling mouth and is analyzed; Control pressurer system is connected with cryogenic high pressure reactor air inlet, guarantees the pressure that the cryogenic high pressure reactor needs; Data collecting system is connected with cryogenic high pressure reactor temperature-measuring port and pressure tap, the acquisition system data.
On relative two sidewalls of described cryogenic thermostat water-bath a pair of visual windows of looking is arranged, relative with a pair of visual windows on the lower sides of reactor body.
Described control pressurer system comprises the piston type barostat, the piston type barostat by the stroke of Electric Machine Control piston to regulate pressure.Described air supply system comprises the bilateral air agreement system, the bilateral air agreement system comprises substitution gas, by substitution gas, two intake valves, two pressure-regulating valves, gas flowmeter and triple valves, switch being communicated with between two-way gas handling system and the piston type barostat by triple valve.
Beneficial effect of the present invention is: a kind of low temperature high pressure gas hydrate replacement reaction kettle of the present invention and system, solved the problem of high pressure rotary sealing poor performance, and have reliable, noiseless advantage.Can also be by the phenomenon that is taken place in the visual windows Real Time Observation reactor, and the gas component of measuring in real time in the hydrate solid by Raman spectrometer changes.
Description of drawings
Fig. 1 is a low temperature high pressure gas hydrate replacement reaction kettle structural representation of the present invention;
Fig. 2 is the CO of cryogenic high pressure reactor of the present invention
2The reaction system figure of gas displacement methane hydrate.
The specific embodiment
Low temperature high pressure gas hydrate replacement reaction kettle structural representation as shown in Figure 1, low temperature high pressure gas hydrate replacement reaction kettle comprises reactor body 14, upper end cover 7, flange 5, agitating device 15, chassis 1, a pair of visual window 4 and several connectors, agitating device 15 comprises motor 13, agitator 16, stirring vane 3, shaft 18, upper end cover 7 adopts flange 5 to be connected with kettle 14, between with 6 sealings of polytetrafluoroethylene (PTFE) (fluoroplastics) pad, on the central boss 17 of upper end cover 7 stirring motor 13 is installed, it is a permanent magnet; Butt joint is equipped with agitator 16 below the central boss 17 of upper end cover 7, itself and stirring motor 13 are in the same center line, stirring motor 13 and agitator 16 connect by the magnetic force coupling, have replaced movable sealing with static seal, have solved the problem of high pressure rotary sealing poor performance.There is stirring vane 3 bottom of the shaft 18 of agitator 16, and the 2nd stirring vane also can be arranged, and it is positioned at the top of first stirring vane 3, and at interval suitably distance in order to liquid in the abundant stirred tank, has chassis 1 in the bottom of kettle 14, in order to fixing kettle 14.The autoclave material can be the 316L stainless steel.Reactor 14 can be suspended on the frame by stirring motor 13 bottoms.The center line unanimity that 4, two windows of a pair of visual windows are arranged on the lower sides of reactor body 14 is to looking state, in order to phenomenon in the observation still.The window material 4a of visual window is a quartz glass, can be withstand voltage to 30MPa.The sealing ring 4b of window adopts viton seal ring, can be low temperature resistant to-20～-30 ℃.Glass window 4a produces pressure by rotation nut 4c and seals with kettle.
The position of several connectors a: inlet 8, pressure tap 9 and 2 air inlet 10a, 10b are arranged on the lateral circle surface that is evenly arranged in flange 5 on the kettle 14, the pressure tap 9 double safety valves of doing, venting, it is arranged on the lateral location of flange 5 of reactor body 14, and radially passes flange and enter in the reactor chamber; Inlet 8 is arranged on the lateral location of flange 5 of reactor body 14, and radially passes flange and enter in the reactor chamber; 2 air inlets adjoin mutually, are arranged on the lateral location of flange 5 of reactor body 14, and radially pass flange and enter in the reactor chamber.Have gas sampling mouth 11 in the side of upper end cover 7, and radially pass upper end cover and vertically enter in the reactor chamber again, this thief hatch double as exhaust outlet is in order to gather gaseous sample or discharging gas reactor.Temperature-measuring port 12 has two, measure the fluid temperature of bottom in the reactor and the gas temperature on top respectively, be arranged symmetrically in the both sides of the central boss 17 of reactor upper end cover 7, and vertically pass the reactor end cap and enter in the chamber, there is temperature sensor screw thread mouth to be installed on the temperature-measuring port 12 in order to connect temperature sensor.In the bottom of kettle 14 leakage fluid dram 2 is arranged, leakage fluid dram 2 is arranged in the reactor body near on the lateral location of bottom, and radially passes the still bottom, upwards vertically enters the recess in center in the reactor chamber in order to liquid in the discharge still again.
Be illustrated in figure 2 as the CO of cryogenic high pressure reactor
2The reaction system figure of gas displacement methane hydrate, low temperature high pressure gas hydrate exchange system comprise cryogenic high pressure reactor, air supply system, gaseous component detection system, vacuum system, cryogenic thermostat water-bath 33, control pressurer system, data collecting system.Reactor immerses in the cryogenic thermostat water-bath 33, keeps the interior fluid temperature of reactor stable; Vacuum system is by vacuumizing in 10 pairs of cryogenic high pressure reactors of air inlet chamber; The gaseous component detection system is carried out gas collecting by gas sampling mouth 11 and is analyzed; Control pressurer system is connected with cryogenic high pressure reactor air inlet 10, guarantees the pressure that the cryogenic high pressure reactor needs; Data collecting system is connected the acquisition system data with cryogenic high pressure reactor temperature-measuring port 12, pressure tap 9.
Described gaseous component detection system comprises gas sampling mouth 11, sampling valve 22, gas collecting bag, gas chromatograph.
Described data collecting system 36 comprises temperature-measuring port 12, pressure tap 9, temperature sensor 32, pressure sensor 31, data acquisition module and data acquisition software and supervisory control comuter.
Described control pressurer system comprises piston type barostat 27, described piston type barostat by the stroke of Electric Machine Control piston to regulate pressure.
Described air supply system comprises the bilateral air agreement system, the bilateral air agreement system comprises substitution gas 29, by substitution gas 28, two intake valves 24,25, two pressure-regulating valves 35, gas flowmeter 37 and triple valves 26, switch being communicated with between two-way gas handling systems and the piston type barostat 27 by triple valve 26.
Described vacuum system comprises vavuum pump 30 and vacuum valve 23, and vacuum system is connected with piston type barostat 27.
Have on relative two sidewalls of described cryogenic thermostat water-bath 33 a pair of to looking visual windows, relative with a pair of visual windows 4 on the lower sides of reactor body 14.
The operating procedure of carrying out the gas hydrate displacement is as follows:
1), before carrying out hydrate generation and displacement reaction, open reactor upper end cover 7 earlier, use redistilled water cleaning reaction still 14 inner chambers and oven dry repeatedly, then a certain amount of distilled water or the solution that is added with additive are injected in the reactor 14, cover upper end cover 7 and good seal, connect systems such as intake and exhaust pipeline again.
2), open vacuum valve 23, to vacuumizing in the reactor chamber, vacuum reaches the regulation requirement in reactor by air inlet 10a, 10b.Close vacuum valve 23 then.Reactor is immersed in the cryogenic thermostat water-bath 33 afterwards, fluid temperature reaches the temperature of regulation in reactor 14, and keeps stable.
3), open intake valve 24, and triple valve 26 turned to intake valve 24 be communicated with, in reactor and piston type barostat 27 cylinders, charge into by substitution gas 28, be adjusted to required pressure by pressure-regulating valve 35.Close intake valve 24 then, by piston type barostat 27 reacting kettle inner pressure is remained on the pressure of regulation afterwards.Open stirring motor 13, be adjusted to required mixing speed, hydrate begins to generate.Keep the still internal pressure constant by the piston type barostat, water all becomes till the hydrate in still; Gas flowmeter on being connected air inlet pipeline shows when the gas air demand no longer changes, and shows that the hydrate generative process finishes.Stop this moment stirring, keep reactor temperature, pressure stability certain hour.Afterwards, open air bleeding valve 21, rapidly with the gas emptying in the reactor to normal pressure, close air bleeding valve 21 then.
5), open vacuum valve 23, fast with in the still and the gases in the piston type barostat 27 extract out, close vacuum valve 23.
6), open another intake valve 25, and triple valve 26 turned to intake valve 25 be communicated with, in reactor and piston type barostat 27 cylinders, charge into substitution gas 29, be adjusted to required pressure by pressure-regulating valve 35.Close intake valve 25 then, by piston type barostat 27 reactor 14 internal pressures are remained on the pressure of regulation afterwards.Open stirring motor 13, be adjusted to required mixing speed, the hydrate replacement process begins.By visual windows 4 can the observing response still in hydrate displacement phenomenon.Open sampling valve 22, carry out the gas primary sample, close sampling valve 22 by gas sampling mouth 11.Afterwards, carry out gas sample at regular intervals at interval, as on gas chromatograph, analyzing its gas component later on.When gas component no longer changed, replacement process finished.
7), last sampling.Open vacuum valve 23, gas in the reactor 14 is evacuated to vacuum rapidly, close vacuum valve 23.Make reactor 14 interior surplus water compounds slightly decomposing under the high-temperature, by pressure signal observed pressure rising situation.After reacting kettle inner pressure is constant, decompose and finish, get gaseous sample by gas sampling mouth 11 and analyze its gaseous component.
8), change the pressure and temperature in the reactor, can under different temperatures pressure, carry out displacement reaction.
Claims (13)
1, a kind of low temperature high pressure gas hydrate replacement reaction kettle, comprise reactor body, upper end cover, flange, agitating device, chassis, a pair of visual windows and several connectors, agitating device comprises motor, agitator, stirring vane, shaft, it is characterized in that, upper end cover adopts flange to be connected with kettle, between with teflon gasket sealing, on the central boss of upper end cover, stirring motor is installed, stirring motor adopts permanent magnet; Butt joint is equipped with agitator below the central boss of upper end cover, itself and stirring motor are in the same center line, stirring motor and agitator connect by the magnetic force coupling, and there is stirring vane the bottom of the shaft of agitator, in order to liquid in the abundant stirred tank, the chassis is arranged at the bottom at kettle, in order to fixing kettle, a pair of visual windows is arranged, the center line unanimity of two windows on the lower sides of reactor body, be looking state, several connectors are positioned at the outside of reactor.
2, low temperature high pressure gas hydrate replacement reaction kettle according to claim 1, it is characterized in that, the window material of described visual window is a quartz glass, and the sealing ring of window adopts viton seal ring, and glass window produces pressure and kettle sealing by the rotation nut.
3, low temperature high pressure gas hydrate replacement reaction kettle according to claim 1 is characterized in that, described stirring vane can be 2, and order is installed on the shaft, at a distance of certain distance.
4, low temperature high pressure gas hydrate replacement reaction kettle according to claim 1 is characterized in that, described several connectors comprise that one group is advanced leakage fluid dram, one group of porting, one group of temperature-measuring port, a pressure tap and a gas sampling mouth.
According to claim 1,4 described low temperature high pressure gas hydrate replacement reaction kettles, it is characterized in that 5, described inlet is arranged on the lateral location of flange of reactor body, and radially pass flange and enter in the reactor chamber; Leakage fluid dram is arranged in the reactor body near on the lateral location of bottom, and radially passes the still bottom, upwards vertically enters the recess in center in the reactor chamber again.
6, according to claim 1,4 described low temperature high pressure gas hydrate replacement reaction kettles, it is characterized in that described air inlet has two, be arranged on the lateral location of flange of reactor body that two air inlets adjoin mutually.
7, according to claim 1,4 described low temperature high pressure gas hydrate replacement reaction kettles, it is characterized in that described gas sampling mouth is arranged in the side of upper end cover, and radially pass upper end cover and vertically enter in the reactor chamber thief hatch double as exhaust outlet again.
8, according to claim 1,4 described low temperature high pressure gas hydrate replacement reaction kettles, it is characterized in that, described temperature-measuring port has two, be arranged symmetrically in the both sides of the central boss of reactor upper end cover, and vertically pass the reactor end cap and enter in the chamber, there is temperature sensor that screw thread mouth is installed on the temperature-measuring port.
According to claim 1,4 described low temperature high pressure gas hydrate replacement reaction kettles, it is characterized in that 9, the double safety valve of doing of described pressure tap is arranged on the lateral location of flange of reactor body, and radially pass flange and enter in the reactor chamber.
10, a kind of low temperature high pressure gas hydrate exchange system, comprise low temperature high pressure gas hydrate replacement reaction kettle, it is characterized in that, also comprise air supply system, gaseous component detection system, vacuum system, cryogenic thermostat water-bath, control pressurer system, data collecting system, reactor immerses in the cryogenic thermostat water-bath, keeps the interior fluid temperature of reactor stable; Vacuum system by air inlet to vacuumizing in the cryogenic high pressure reactor chamber; The gaseous component detection system is carried out gas collecting by the gas sampling mouth and is analyzed; Control pressurer system is connected with cryogenic high pressure reactor air inlet, guarantees the pressure that the cryogenic high pressure reactor needs; Data collecting system is connected with cryogenic high pressure reactor temperature-measuring port and pressure tap, the acquisition system data.
11, low temperature high pressure gas hydrate exchange system according to claim 10 is characterized in that, on relative two sidewalls of described cryogenic thermostat water-bath a pair of visual windows of looking is arranged, and is relative with a pair of visual windows on the lower sides of reactor body.
12, low temperature high pressure gas hydrate exchange system according to claim 10 is characterized in that, described control pressurer system comprises the piston type barostat, the piston type barostat by the stroke of Electric Machine Control piston to regulate pressure.
13, according to claim 10,12 described low temperature high pressure gas hydrate exchange systems, it is characterized in that, described air supply system comprises the bilateral air agreement system, the bilateral air agreement system comprises substitution gas, by substitution gas, two intake valves, two pressure-regulating valves, gas flowmeter and triple valves, switch being communicated with between two-way gas handling system and the piston type barostat by triple valve.
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