CN108295777A - A kind of gas hydrate reinforcing generation method - Google Patents
A kind of gas hydrate reinforcing generation method Download PDFInfo
- Publication number
- CN108295777A CN108295777A CN201810289070.1A CN201810289070A CN108295777A CN 108295777 A CN108295777 A CN 108295777A CN 201810289070 A CN201810289070 A CN 201810289070A CN 108295777 A CN108295777 A CN 108295777A
- Authority
- CN
- China
- Prior art keywords
- gas
- hydrate
- reaction
- generation method
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 39
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000003014 reinforcing effect Effects 0.000 title description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 45
- 239000000945 filler Substances 0.000 claims abstract description 43
- 239000006260 foam Substances 0.000 claims abstract description 43
- 239000000919 ceramic Substances 0.000 claims abstract description 39
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006703 hydration reaction Methods 0.000 claims abstract description 30
- 239000012495 reaction gas Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 13
- 238000012856 packing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 230000003247 decreasing effect Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- 150000004677 hydrates Chemical class 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 230000006698 induction Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 229960004424 carbon dioxide Drugs 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
Abstract
The invention discloses a kind of gas hydrates to strengthen generation method, including：Water, foam silicon carbide ceramics filler are mixed, it is contacted in closed reaction kettle with reaction gas is waited for, it reacts under conditions of hydrate generates, waits for that with water on foam silicon carbide ceramics filler surface and pore interior hydration reaction occurs for reaction gas, generate gas hydrate.The present invention improves mass-transfer efficiency between liquid phase, accelerate hydration reaction speed, improve gas-storing capacity, evade dynamic contract-enhanced technology and needs the complicated machinery solved and high energy consumption issues, reduce energy consumption and maintenance of machine cost, and used filler can reuse, and have good industrial applications foreground.
Description
Technical field
The present invention relates to gas hydrate synthesis technical field, especially a kind of gas hydrate strengthens generation method.
Background technology
Gas hydrate is formed with water phase interaction by gas or volatile liquid under certain temperature and pressure condition
A kind of white crystals cage modle substance.Based on the industrial technology of hydrate gas storage and transportation with detach, sea water desalination, greenhouse gases
Capture, Automatic-cooling etc. have important application foreground, become research hotspot in recent years.However, these technologies are most of
Still in the laboratory research stage, the pilot scale stage is partly had been enter into, the main bottleneck for restricting its commercial applications is hydrate
Nucleation induction time is long, the speed of growth is slow, and there is an urgent need to develop the reinforcings of the hydrate of some novel clean and effectives, Applied economy
Generation technique.
Hydrate strengthens generation technique and is divided into dynamic contract-enhanced and two classes of static reinforcing.Dynamic contract-enhanced technology includes stirring, drum
Bubble, spraying, centrifugal rotation hypergravity etc. can improve hydrate formation speed by strengthening mass transfer, but need to additionally introduce
Mechanical equipment and energy consumption, and have in it limited resource, industry amplification application is restricted.Static reinforcement technique is mainly logical
Addition chemical promoter is crossed with porous media filler to promote hydrate growth.It on the one hand, can by adding surfactant
The surface tension for reducing gas-liquid interface, realizes quickly generating for gas hydrate；On the other hand, by add quartz sand, silica gel,
Hydrogel, nanotube, foam stuffing etc. have the porous material of high-specific surface area, increase gas-liquid contact face, to improve hydration
Object growth kinetics.Compared with chemical promoter, porous material have it is environmental-friendly and can iterative cycles the advantages such as utilize, therefore
It receives much attention in recent years.
For example, at Chinese patent CN104785085A " a kind of gas separating method and piece-rate system based on porous material "
In, using nanoscale mesoporous material (aperture 5-50nm), hydrate reaction is carried out at a temperature of 10-15 DEG C, to gas with various into
Row separation, and decomposition of hydrate is carried out at 25-30 DEG C, reaction system moisture content is maintained at 70-80% in entire reaction process.
Since the reaction time is than more random, there is uncontrollable gas flow rate in this method, reaction channel may be generated hydrate and block up
In place of the deficiencies of plug.Chinese patent literature CN101863483A " a kind of the solid carbon dioxide of gas hydrate and preparation method thereof "
In, hydrate induction time is shortened using solid carbon dioxide (3-15 μm of size), i.e., by hydrophobicity aerosil with water high-strength
A kind of powdered, flowable powder packet aqueous mixtures are formed after degree blender high speed shearing, realize the high degree of dispersion of water.It should
Method can increase air-water contact area, but there are still challenge, industry in terms of preserving transport and repeat performance for solid carbon dioxide
Extension is somewhat limited.It is " a kind of to utilize hydrophobically modified foam metal in Chinese patent literature CN107551954A
In the method for realizing fast hydrating gas storage ", the heat conduction skeleton using hydrophobically modified foam metal as static hydrated body system, in 3-
At a temperature of 30MPa pressure and 0-20 DEG C, hydrate reaction occurs to achieve the purpose that gas stores.However, due to metal material
The chemical property of material itself is more active, uses for a long time it is possible that situations such as corrosion-deformation, this method is not suitable for acid
The commercial Application of property gas or seawer system.
Therefore, the novel porous materials that strengthened aqua compound generates are used for, need to consider to improve mass-transfer efficiency and time shift
Except hydrate reaction generates the factors such as heat, acid-alkali-corrosive-resisting, overcome the deficiencies in the prior art.
Invention content
It is a primary object of the present invention to overcome the deficiencies of the prior art and provide a kind of gas hydrate reinforcing generation side
Method.
To achieve the above object, the present invention uses following technical scheme：
A kind of gas hydrate reinforcing generation method, including：Water, foam silicon carbide ceramics filler are mixed, closed
It contacts with reaction gas is waited in reaction kettle, reacts under conditions of hydrate generates, wait for reaction gas with water in the carbon
Hydration reaction occurs for SiClx ceramic foam packing surface and pore interior, generates gas hydrate.
Further：
It is described to wait for that reaction gas includes methane, ethane, ethylene, propane, nitrogen, oxygen, carbon monoxide, carbon dioxide or hydrogen
One or more of gas.
Include the following steps：
A, in high voltage bearing closed reactor, foam silicon carbide ceramics filler is added, injects water/aqueous solution, enables filler
It is immersed in water/aqueous solution；
B, wait for reaction gas to specified pressure described in being filled in the reaction kettle；
C, the temperature in the reaction kettle is continuously decreased to particular value, and gas phase is enabled to be generated in hydrate with liquid phase reactor object
It is contacted under temperature and pressure condition, hydration reaction occurs so that the gas pressure in the reaction kettle is gradually reduced, and is finally obtained
Gas hydrate.
In step B, first wait for that reaction gas purges three times to drain air in the reaction kettle with the described of 0.5~1MPa,
Then wait for reaction gas to specified pressure described in being re-filled with.
Include the following steps：
D, it waits for that hydrate growth finishes, after realizing gas separation or gas storage and transportation, hydrate-ceramic foam packing is mixed
Object heats up, and so that hydrate is decomposed reaction, obtains the mixed system of filler and water, thus to foam silicon carbide ceramics filler into
Row recycling repeats the recycled for multiple times that above step realizes filler.
In step, in the water or aqueous solution containing being useful for the active accelerating agent of enhancing solution surface and/or for dropping
The accelerating agent of low hydration reaction pressure.
In step, lauryl sodium sulfate (SDS) solution of a concentration of 300ppm is added in the water or aqueous solution.
The foam silicon carbide ceramics filler is that the carborundum powder containing sintering aid and adhesive are reconciled into slurry leaching
It hangs in polyurethane foam, is sintered at 1500-2200 DEG C after solidification is dry.
In step, the foam silicon carbide ceramics filler micropore size be 0.1mm-5mm, shape be bulk granular or
Monoblock structured packing.
In step C, the temperature in the reaction kettle is 0~5 DEG C, and the pressure in the reaction kettle is 4~20MPa.
In step D, the temperature in the reaction kettle is 15~40 DEG C, and the pressure in the reaction kettle is 0~10MPa.
The gas hydrate of the present invention strengthens generation method, using the large specific surface area of ceramic foam packing, porosity it is high,
The features such as thermal coefficient is big shortens the induction time of hydration reaction generation, realizes the quick removal of hydration reaction heat, promotes gas
The generation of gas hydrate.
Aqueous solution of the present invention using pure water or containing hydration thermodynamic accelerating agent is steeped as hydration reaction system with silicon carbide
Foam ceramics are porous aggregate, filler are immersed in water or aqueous solution, and be filled with the gas of certain pressure, inside filler each
Micropore is all equivalent to one " high-pressure mini reactor ".In closed reaction vessel, when temperature is reduced to hydrate reaction item
Part, after one section of induction time, water takes place hydration reaction with gas and generates hydrate, and container inner pressure disappears with gas
It consumes and reduces.The large specific surface area of filler is capable of providing more hydrate nucleation sites with uniform pore structure, effectively
Shorten reaction induction time, and the heat transfer coefficient that filler is significantly larger than hydrate itself makes it during the reaction by reaction heat
It passes in time, reduces the inhibiting effect to hydration reaction caused by temperature rise, improve reaction speed.Additionally by
The motive force of hydration reaction can be changed by adjusting temperature and initial pressure, to control the speed of hydrate generation.Silicon carbide steeps
The advantageous property of foam ceramics can be repeated quickly and easily as many times as required use, by the process that the generation that repeatedly cools down-heating is decomposed, still can
It keeps preferable and strengthens performance.
In preferred embodiment, foam silicon carbide ceramics filler used in the present invention is will be containing the silicon carbide of sintering aid
Powder reconciles into slurry leaching with adhesive and hangs in polyurethane foam, is sintered at 1500-2200 DEG C after solidification is dry, as a result,
In addition to having the characteristics that the pore distribution of foamed ceramics is uniform, the porosity is high, relative density is small, large specific surface area, silicon carbide bubble
Foam ceramics also have that high temperature resistant, anti-oxidant, acid-alkali-corrosive-resisting, coefficient of thermal expansion is small, thermal conductivity is big, hardness is high, anti-thermal shock etc. is excellent
Benign energy.On the one hand, the pore structure being connected to inside foam silicon carbide ceramics can pass through the transmission of change gas and hydrone
Path enhances gas-liquid mass transfer, and on the other hand its larger thermal conductivity can effectively remove the heat of hydrate reaction generation
Amount, to be conducive to the generation of gas hydrate.
The present invention provides simple, the efficient hydrate based on foam silicon carbide ceramics filler and strengthens generation method, by carbon
SiClx ceramic foam packing, water are simultaneously preferably added to hydrate accelerant mixing, and with the gases such as methane under specific Temperature-pressure Conditions
Contact removes hydration reaction and generates heat, accelerate hydration reaction speed, improve gas storage to improve mass-transfer efficiency between liquid phase
Amount has evaded dynamic contract-enhanced technology and has needed the complicated machinery that solves and high energy consumption issues, for commercial Application in future provide basis and
It helps.
First Application foam silicon carbide ceramics filler of the present invention accelerates growth of aerial hydrate dynamic process.In addition to tool
The features such as pore distribution of standby porous material is uniform, the porosity is high, relative density is small, large specific surface area, which is also equipped with pottery
The Optimalities such as the high temperature resistant of ceramic material, anti-oxidant, acid-alkali-corrosive-resisting, coefficient of thermal expansion is small, thermal conductivity is big, hardness is high, anti-thermal shock
Energy.For example, the material thermal conductivity (140W m-1 K-1) is more than 200 times of hydrate (about 0.6W m-1 K-1), Ke Yiyou
Effect removes the heat that hydrate reaction generates and is conducive to the quick progress of hydration reaction to accelerate reaction speed.The invention belongs to
It is simple and practicable in gas hydrate static state reinforcement technique scope, can save the dynamic contract-enhanceds technology such as Mixing Machine equipment design,
The expenses such as device maintenance, energy consumption, and foam silicon carbide ceramics filler Repeatability is good, and can carry out repeatedly recycling makes
With recycling reduces operating cost, has the advantages such as economy, efficiency, controllable.
Hydrate provided by the invention based on foam silicon carbide ceramics filler strengthens generation method, is filled in reaction kettle
There is foam silicon carbide ceramics filler, the features such as using ceramic foam packing porosity height, large specific surface area, high thermal conductivity, reinforces
Two-phase mass transfer provides more polyhydrate nucleation site, accelerates the removal of hydration reaction heat.The use of filler can effectively shorten gas
The hydration reaction induction time that body occurs with water was foreshortened to 7.5 hours average by 28.0 hours；Maximum reaction velocity is by 4.0m3m-3min-1It is promoted to 5.0-6.5m3m-3min-1, the conversion ratio of water also risen.Meanwhile foam silicon carbide ceramics have intensity
Feature high, hardness is big, can be by being repeatedly used after heating recovery and keeping excellent in performance, it is contemplated that will reduce work
Industry application cost, has broad application prospects.
Description of the drawings
Fig. 1 is the structural schematic diagram for strengthening the device of generation method for implementing the gas hydrate of the embodiment of the present invention.
During Fig. 2 is 6 cooling synthesis-heating Decomposition Cycle, filler, dodecyl sodium sulfate (SDS, 300ppm) are molten
The induction time of hydration reaction occurs every time for liquid and methane gas, and it is not filled when hydration reaction induction time comparison
Figure.
During Fig. 3 is 6 cooling synthesis-heating Decomposition Cycle, filler, SDS (300ppm) solution and methane gas are every
The secondary water conversion ratio that hydration reaction occurs, and it is not filled when the water conversion ratio comparison diagram that reacts.
During Fig. 4 is 6 cooling synthesis-heating Decomposition Cycle, filler, SDS (300ppm) solution and methane gas are every
It is secondary occur hydration reaction maximum reaction rate, and it is not filled when maximum reaction rate comparison diagram.
Reference sign：
1, gas bomb；2, constant temperature water bath；3, reaction kettle；4, air inlet；5, gas outlet；6, temperature sensor；7, pressure
Sensor；8, data collecting system.
Specific implementation mode
It elaborates below to embodiments of the present invention.It is emphasized that following the description is only exemplary,
The range being not intended to be limiting of the invention and its application.
In one embodiment, a kind of hydrate based on foam silicon carbide ceramics filler strengthens generation method, wraps successively
Include following steps：
Step A, in high voltage bearing closed reactor, enough foam silicon carbide ceramics fillers, injection water/water-soluble is added
Liquid enables filler be immersed in water/aqueous solution；
Step B, it is purged three times to drain air in kettle with the gas of 0.5~1MPa, is then charged with the gas to specific pressure
Power；
Step C, temperature is continuously decreased to particular value, enables gas phase with liquid phase reactor object at certain temperature and pressure condition
Contact occurs hydration reaction and gas in container pressure is gradually reduced, finally obtains gas hydrate；
Step D, wait for that hydrate growth finishes, it, can be by the hydrate-foamed ceramics after realizing gas separation or gas storage and transportation
Filler mixture heats up, and so that hydrate is decomposed reaction, obtains the mixed system of filler and water, to sic foam pottery
Porcelain filling carries out recycling or repeating the recycled for multiple times that above step realizes filler.
As shown in Figure 1, a kind of gas hydrate for implementing the embodiment of the present invention strengthens the device of generation method, packet
It includes：Gas bomb 1, constant temperature water bath 2, reaction kettle 3, air inlet 4, gas outlet 5, temperature sensor 6, pressure sensor 7, data are adopted
Collecting system 8.
Temperature sensor 6 and pressure sensor 7 are respectively used to be monitored temperature T, the pressure P in reaction kettle 3, by it
It is transmitted to data collecting system 8.Preferably, which includes the gas phase temperature and liquidus temperature measured respectively in reaction kettle 3
Two temperature sensors 6.
In a preferred embodiment, in step, contain in the aqueous solution and be useful for the enhancing active accelerating agent of solution surface
And/or the accelerating agent for reducing hydration reaction pressure.
In a preferred embodiment, in step, the foam silicon carbide ceramics filler micropore size is 0.1mm-5mm, shape
Shape can be bulk granular or monoblock structured packing.
In a preferred embodiment, in stepb, the gas includes methane, ethane, ethylene, propane, nitrogen, oxygen, one
It is one or more in carbonoxide, carbon dioxide or hydrogen.
In a preferred embodiment, in step C, when carrying out the hydration reaction, the temperature in the reaction kettle is 0~5
℃；
In a preferred embodiment, in step D, when carrying out the decomposition reaction, temperature in the reaction kettle is 15~
40℃；
In a preferred embodiment, in stepb, when carrying out the hydration reaction, pressure in the reaction kettle is 4~
20MPa；
In a preferred embodiment, in step D, when carrying out the decomposition reaction, pressure in the reaction kettle is 0~
10MPa。
Embodiment one：
A kind of hydrate reinforcing generation method based on foam silicon carbide ceramics filler is present embodiments provided, this method makes
High pressure low temperature reaction kettle, internal diameter 50mm, dischargeable capacity 100mL, pressure-resistant 20MPa.It is as follows：
Step A, in high voltage bearing closed reactor, 30 milliliters of water/aqueous solution is added, 9.84g sic foams are made pottery
Porcelain filling is immersed in water/aqueous solution.In the present embodiment, foam silicon carbide ceramics filler dissipates landfill using ball graininess
Material, grain size about 6mm, aperture 1.0-1.5mm；
Step B, it is purged three times to drain air in kettle with the gas of 0.5~1MPa, adjusts the temperature to 15 DEG C, then proceed to
Gas is filled with to specified pressure and remains stable, in the present embodiment, gas is methane, is forced into 7.9MPa；
Step C, temperature is continuously decreased to particular value, enables gas phase with liquid phase reactor object at certain temperature and pressure condition
Contact, gas-liquid generation hydration reaction makes gas in container pressure be gradually reduced after a period of time, finally obtains and contains a large amount of gas
The hydrate of body.In the present embodiment, 2 DEG C are cooled to, obtains methane hydrate after reaction；
Step D, hydration reaction occurs for methane and water, and pressure stops declining and remains stable after a period of time, reacts at this time
Terminate.Reuse number for research influences caused by carrier performance, and the hydrate-ceramic foam packing mixture is gradual
It is warming up to 15 DEG C, hydrate is decomposed reaction at this temperature, obtains the mixed system of filler and water；
Step E, repeat step C and step D, in the present embodiment, number of repetition is 6 times.
In order to accelerate hydration reaction speed, surfactant can be added in aqueous solution and live for enhancing solution surface
Property, or the accelerating agent of hydration reaction pressure is reduced, such as lauryl sodium sulfate (SDS) solution using a concentration of 300ppm
It is reacted.
As shown in figs 2-4, " r1-r6 " indicates 6 cooling synthesis-heating Decomposition Cycles to the present embodiment experimental result respectively
Process, experimental result when " control " indicates not adding foam silicon carbide ceramics filler.From the point of view of experimental result, the addition of filler
So that the probability that hydration reaction occurs in 30 hours for methane and water is become larger, substantially reduces induction time, dropped to by 28 hours
It is 7.5 hours average.Meanwhile reaction rate and water conversion ratio are also promoted, and the performance of filler does not occur after multiplicating
Decline.This is attributed to the fact that the larger specific surface area of filler can provide more nucleation site, so as to shorten the induction time of reaction；
Larger thermal coefficient can pass hydration reaction heat quickly, therefore the conversion ratio of reaction rate and water is risen,
The Repeatability of filler will preferably be attributed to the fact that the stronger mechanical performance of carbofrax material itself and the stabilization chemical property of acid and alkali-resistance.
Experimental results embody the notable invigoration effect that foam silicon carbide ceramics filler generates gas hydrate.
Strengthen generation method using the gas hydrate based on foam silicon carbide ceramics filler of the present invention, advantageously accounts for
The problems such as existing hydrate induction time is long, generating rate is low.This method is that appropriate silicon carbide is placed in closed reaction kettle
Water and a small amount of hydrate formation promoter (such as lauryl sodium sulfate) is added, after being come into full contact with filler in ceramic foam packing
It is filled with gas, in 0-5 DEG C and gas hydrate under 4-20MPa.The silicon carbide foam ceramic material that the present invention uses is led
Hot coefficient (140W m-1 K-1) is more than 200 times of hydrate (about 0.6W m-1 K-1), can effectively remove hydrate reaction
The heat of generation, to be conducive to the quick progress of reaction；And foamed material large specific surface area, the porosity are high, pore distribution is equal
The features such as even, can increase gas liquid interfacial area, provide more polyhydrate nucleation site.It is demonstrated experimentally that the present invention can be by hydrate
It is nucleated induction time and shortens 52.4%-90.1%, hydrate formation speed improves 7.90%-29.8%, hydrate formation
The conversion ratio of middle water promotes 15.9%-68.0%. compared with the tradition such as stirring, spraying strengthen generation technique, and low energy consumption for this method,
It designs, can expand for sea water desalination, flue gas separation, greenhouse gases are sealed up for safekeeping, sewage disposal etc. is multiple is based on without complex device
The new technique field of hydrate.
The device of the invention is simple and efficient, and be can help to Hydrate Technology and is caught in gas storage and transportation, sea water desalination, greenhouse gases
The development and application of obtain etc., reduce energy consumption and maintenance of machine cost, there is good industrial applications foreground.
The above content is specific/preferred embodiment further description made for the present invention is combined, cannot recognize
The specific implementation of the fixed present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs,
Without departing from the inventive concept of the premise, some replacements or modification can also be made to the embodiment that these have been described,
And these are substituted or variant all shall be regarded as belonging to protection scope of the present invention.
Claims (10)
1. a kind of gas hydrate strengthens generation method, which is characterized in that including：Water, foam silicon carbide ceramics filler are mixed,
It is contacted in closed reaction kettle with reaction gas is waited for, reacts under conditions of hydrate generates, wait for reaction gas and water
Hydration reaction occurs on foam silicon carbide ceramics filler surface and pore interior, generates gas hydrate.
2. gas hydrate as described in claim 1 strengthens generation method, which is characterized in that described to wait for that reaction gas includes first
One or more of alkane, ethane, ethylene, propane, nitrogen, oxygen, carbon monoxide, carbon dioxide or hydrogen.
3. gas hydrate as claimed in claim 1 or 2 strengthens generation method, which is characterized in that include the following steps：
A, in high voltage bearing closed reactor, foam silicon carbide ceramics filler is added, injects water/aqueous solution, filler is enabled to submerge
In water/aqueous solution；
B, wait for reaction gas to specified pressure described in being filled in the reaction kettle；
C, temperature in the reaction kettle is continuously decreased to particular value, the temperature for enabling gas phase be generated in hydrate with liquid phase reactor object
With contacted under pressure condition, occur hydration reaction so that the gas pressure in the reaction kettle is gradually reduced, and finally obtains gas
Hydrate.
4. gas hydrate as claimed in claim 3 strengthens generation method, which is characterized in that in step B, first with 0.5~
The described of 1MPa waits for that reaction gas purges three times to drain air in the reaction kettle, is then re-filled with and described waits for reaction gas extremely
Specified pressure.
5. gas hydrate as claimed in claim 3 strengthens generation method, which is characterized in that include the following steps：
D, wait for that hydrate growth finishes, after realizing gas separation or gas storage and transportation, by hydrate-ceramic foam packing mixture liter
Temperature makes hydrate decompose reaction, obtains the mixed system of filler and water, to be returned to foam silicon carbide ceramics filler
Receive or repeat the recycled for multiple times that above step realizes filler.
6. as claim 3 to 5 any one of them gas hydrate strengthens generation method, which is characterized in that in step,
Contain in the water or aqueous solution and is useful for the active accelerating agent of enhancing solution surface and/or the rush for reducing hydration reaction pressure
Into agent, it is preferable that lauryl sodium sulfate (SDS) solution of a concentration of 300ppm is added in the water or aqueous solution.
7. as claim 3 to 6 any one of them gas hydrate strengthens generation method, which is characterized in that the silicon carbide
Ceramic foam packing be the carborundum powder containing sintering aid and adhesive are reconciled into slurry leaching to hang in polyurethane foam, Gu
It is sintered at 1500-2200 DEG C after changing drying.
8. as claim 3 to 7 any one of them gas hydrate strengthens generation method, which is characterized in that in step,
The foam silicon carbide ceramics filler micropore size is 0.1mm-5mm, and shape is bulk granular or monoblock structured packing.
9. as claim 3 to 8 any one of them gas hydrate strengthens generation method, which is characterized in that in step C,
Temperature in the reaction kettle is 0~5 DEG C, and the pressure in the reaction kettle is 4~20MPa.
10. gas hydrate as claimed in claim 5 strengthens generation method, which is characterized in that in step D, the reaction
Temperature in kettle is 15~40 DEG C, and the pressure in the reaction kettle is 0~10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810289070.1A CN108295777A (en) | 2018-03-30 | 2018-03-30 | A kind of gas hydrate reinforcing generation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810289070.1A CN108295777A (en) | 2018-03-30 | 2018-03-30 | A kind of gas hydrate reinforcing generation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108295777A true CN108295777A (en) | 2018-07-20 |
Family
ID=62846952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810289070.1A Pending CN108295777A (en) | 2018-03-30 | 2018-03-30 | A kind of gas hydrate reinforcing generation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108295777A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124660A1 (en) * | 2018-12-18 | 2020-06-25 | 中国科学院广州能源研究所 | Method for storing natural gas hydrate |
| CN113307403A (en) * | 2021-05-26 | 2021-08-27 | 青岛科技大学 | Seawater desalination device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986490A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High strength and high toughness foamed SiC/Al material and its preparing method |
| US20090028776A1 (en) * | 2006-06-08 | 2009-01-29 | Osegovic John P | Seawater-based carbon dioxide disposal |
| CN101592432A (en) * | 2009-07-08 | 2009-12-02 | 黑龙江科技学院 | The promotion method that a kind of coal mine mash gas mixture hydration curing separates |
| CN102218293A (en) * | 2010-04-14 | 2011-10-19 | 中国科学院金属研究所 | Silicon carbide foamed ceramics corrugated structured packing and preparation method and applications thereof |
| CN104785085A (en) * | 2015-03-26 | 2015-07-22 | 太原理工大学 | Gas separation method based on porous material and separation system |
-
2018
- 2018-03-30 CN CN201810289070.1A patent/CN108295777A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986490A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High strength and high toughness foamed SiC/Al material and its preparing method |
| US20090028776A1 (en) * | 2006-06-08 | 2009-01-29 | Osegovic John P | Seawater-based carbon dioxide disposal |
| CN101592432A (en) * | 2009-07-08 | 2009-12-02 | 黑龙江科技学院 | The promotion method that a kind of coal mine mash gas mixture hydration curing separates |
| CN102218293A (en) * | 2010-04-14 | 2011-10-19 | 中国科学院金属研究所 | Silicon carbide foamed ceramics corrugated structured packing and preparation method and applications thereof |
| CN104785085A (en) * | 2015-03-26 | 2015-07-22 | 太原理工大学 | Gas separation method based on porous material and separation system |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124660A1 (en) * | 2018-12-18 | 2020-06-25 | 中国科学院广州能源研究所 | Method for storing natural gas hydrate |
| CN113307403A (en) * | 2021-05-26 | 2021-08-27 | 青岛科技大学 | Seawater desalination device |
| CN113307403B (en) * | 2021-05-26 | 2022-06-03 | 青岛科技大学 | Seawater desalination device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Preparation, properties and applications of fly ash-based porous geopolymers: A review | |
| Li et al. | CO2 capture from binary mixture via forming hydrate with the help of tetra-n-butyl ammonium bromide | |
| CN105439563B (en) | A kind of monolithic porous carbon fiber reinforced silicon carbide matrix composite and its preparation and application | |
| JP3591724B2 (en) | Carbon dioxide absorber and carbon dioxide separator | |
| AU2011317414B2 (en) | Device for collecting solar energy | |
| US7402198B2 (en) | Carbon dioxide adsorption-desorption material and adsorption-desorption apparatus | |
| CN108295777A (en) | A kind of gas hydrate reinforcing generation method | |
| Liu et al. | A review on thermal properties improvement of phase change materials and its combination with solar thermal energy storage | |
| CN105964193A (en) | Method for preparing graphene oxide-alumina composite aerogel | |
| CN113773064B (en) | Porous ceramic with hierarchical pore structure | |
| CN111841634B (en) | Sponge carrier catalyst for catalytic hydrolysis hydrogen production and preparation method and application thereof | |
| CN108854928A (en) | Preparation method preparing hydrogen by ammonia decomposition reaction and separate economic benefits and social benefits ceramic of compact membrane reactor | |
| CN108855187A (en) | A kind of fluorine richness boron carbon nitrogen catalysis material and its application in efficiently reduction carbon dioxide | |
| CN113130880A (en) | Preparation method of positive electrode sulfur-fixing carrier material of lithium-sulfur battery | |
| CN106753264A (en) | Standby mesoporous manosil AS alkali sizing phase-change material of a kind of utilization coal ash for manufacturing and preparation method thereof | |
| CN110950421B (en) | MgO micro-sphere with high specific surface area and preparation method and application thereof | |
| EP2644679B1 (en) | Chemical heat accumulator and method for producing same | |
| CN212640401U (en) | Skid-mounted solid hydrate preparation and storage device | |
| Guo et al. | Mechanical stability and heat transfer improvement of CaO-based composite pellets for thermochemical energy storage | |
| KR100828704B1 (en) | Thermal siphon reactor and a hydrogen generator having the same | |
| CN208177427U (en) | A kind of gas hydrate reinforcing generating means | |
| Gokon et al. | Double-walled reformer tubes using high-temperature thermal storage of molten-salt/MgO composite for solar cavity-type reformer | |
| Derevschikov et al. | CaO/Y2O3 pellets for reversible CO2 capture in sorption enhanced reforming process. | |
| JP2011057457A (en) | Hydrogen occlusion method, hydrogen occlusion apparatus and hydrogen occluding carbon material | |
| JP3396642B2 (en) | Carbon dioxide absorber, carbon dioxide separation method, and carbon dioxide separator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |