CN104888673B - Oxidized graphene gas hydrate accelerant and preparation method thereof - Google Patents
Oxidized graphene gas hydrate accelerant and preparation method thereof Download PDFInfo
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- CN104888673B CN104888673B CN201510258514.1A CN201510258514A CN104888673B CN 104888673 B CN104888673 B CN 104888673B CN 201510258514 A CN201510258514 A CN 201510258514A CN 104888673 B CN104888673 B CN 104888673B
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Abstract
The invention belongs to the technical field of generation and utilization of a gas hydrate, specifically discloses a purpose of oxidized graphene powder in preparing a gas hydrate accelerant, and discloses an oxidized graphene gas hydrate accelerant and a preparation method of the oxidized graphene gas hydrate accelerant. The oxidized graphene gas hydrate accelerant is a dispersion liquid of oxidized graphene, wherein the dispersion liquid comprises, by mass percentage: 0.1-1% of graphene, and 0.3-3.5% of sodium chloride, with the balance being distilled water. The accelerant can further be used for accelerating generation of other gas hydrates, such as hydrates of natural gas, carbon dioxide, and oxygen. The accelerant is good in effect of generating and accelerating the hydrate, wide in application, low in cost, and less in use amount. The condition for generating the hydrate is lowered and the time is shortened; the gas storage capacity is increased; and the economic benefit for producing hydrates is effectively improved.
Description
Technical field
The present invention relates to gas hydrate generates and utilizes technical field, refer in particular to a kind of acceleration methane gas gas hydrate synthesis
New accelerator.The generation that can also be used for other gas hydrates such as natural gas, carbon dioxide, oxygen promotes.
Background technology
At present, not only developed rapidly in the energy, field of Environment Protection based on the new technology development of gas hydrate application, Er Qie
Some other field also achieves major progress, and the solid-state conveying of such as natural gas and storage, gas hydrates are as automobile-used
Fuel, based on new separation technology (desalination technology, the concentration of aqueous organopolysiloxane, the admixture of gas generating hydrate
Separate and near critical and supercritical extraction etc.) and the biological engineering based on hydrate and field of new etc..But hydrate exists
These fields application with gas hydrate generate suppression closely bound up with facilitation, by its gas storage density low, generation
Speed is slow and the obstruction of the factor such as induction time length, and the maximum technology barrier that especially current Application of Hydrate technology faces is exactly
How to improve generating rate and the efficiency of hydrate.Such as methane in static pure aquatic system pressure be 5.76mpa, temperature is
When 4.3 DEG C, more than 28 hours, the speed of growth of hydrate crystal directly affects hydrate to the induction time forming hydrate slowly
Popularization using technology.For solving these problems, employ multiple methods and promote the formation of hydrates (woods Yu La etc., chemical industry enters
Exhibition, 2005,24(11): 1229-1233): the speed of growth of hydrate can be improved by stirring, but stirring brings again
Some other unfavorable factors: energy expenditure increases, hydrate gas storage density reduces etc.；Using ultrasonic atomization, increase air-water and connect
Contacting surface is amassed, and can improve hydrate formation speed, but the soniclizer that system is added not only makes investment cost increase, and
And operating cost also increases；Spray and bubble method can increase phase contact area, thus improving hydrate formation speed；In hydrate
Adding some additives in formation system can promote hydrate to generate, and improve hydrate growth speed, research is more both at home and abroad
Be interpolation anion surfactant, such as sodium lauryl sulphate (sds), oxolane (thf), detergent alkylate in water
Sodium sulfonate (sdbs), APG (apg) and tween series of surfactants and composite additive etc..Hydration can be made
Thing forms induction time and shortens to 1～1.5 hour, and pressure reduces by 1～2 mpa compared with pure aquatic system.However, this kind of surfactant
Although hydrate formation speed can be made to accelerate, but unsatisfactory, and hydrate gas storage density is not high.Therefore, study
Novel hydrates generate accelerator, are the only ways of propulsion hydrate industrialization.
Content of the invention
The purpose of the present invention is to provide a kind of novel hydrates accelerator graphene oxide powder for the deficiencies in the prior art
Body, present invention process is simple, with low cost, operating condition is easily-controllable, can significantly improve hydrate generating rate.
In recent years, the Superhydrophilic of Graphene receives the extensive concern of people as a kind of very special phenomenon.Super
Hydrophilic surface refers to the surface with 5 ° of the contact angle ＜ of water, its excellent performance, is widely used, it is possible to achieve self-cleaning surface,
Improve the several functions such as surface heat exchanger effectiveness.Graphene is similar to graphite surface, can adsorb and be desorbed various atoms and molecule.
There is high intensity, high conductivity, high-specific surface area, high-termal conductivity.The feature of graphene oxide structural model is mono-layer oxidized stone
Mertenyl this holding planar structure, carbon-carbon double bond forms similar aromatic ring structure, and is connected with hydroxyl and epoxy radicals both functional groups,
Edge in planar structure also has part carboxyl simultaneously, and the presence of carboxyl and hydroxyl makes itself and water molecule energy form hydrogen bond.
In graphene oxide containing chemical groups such as carboxyl, hydroxyl, carboxyl and epoxy radicals so that graphene oxide have extremely strong hydrophilic
Property, there is good wettability and surface activity.Micro-oxidation Graphene can be added according to these characteristics in water, to increase
The contact area and gas of strong natural gas and hydrone dissolubility in the liquid phase and the formation of hydrogen bond, accelerate gas hydrate
Generating rate.In addition, the heat conductivity that graphene oxide projects also accelerates the heat transfer of hydrate reaction of formation so that heat
Amount can be evacuated rapidly, and when hydrate is in air-water Surface Creation, its good heat conductivity can accelerate thermal diffusion effect,
So that the latent heat that generation hydrate is discharged does not affect the growth of hydrate.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
Purposes in preparing gas hydrate accelerant for the graphene oxide powder.
A kind of graphene oxide gas hydrate accelerant, is graphene oxide dispersion, wherein Graphene (solid) matter
0.1% ~ 1%, sodium chloride (nacl) weight/mass percentage composition is 0.3 ~ 3.5% to amount percentage composition, and remaining is distilled water.
The preparation method of described gas hydrate accelerant is: using graphene oxide powder and the sodium chloride as solvent
(nacl) mix and blend, then it is configured to graphene oxide dispersion with distilled water.
Described graphene oxide powder can with particle diameter be 325 mesh graphite microparticles as raw material, using hummers method preparation
Obtain.
The preparation facilitiess that the present invention adopts include gas cylinder, pressure regulator valve, mass flowmenter, control valve, vacuum pump, pressure
Power, temperature transmitter, water bath with thermostatic control, tank, reactor, data collecting system, computer etc..By gas cylinder as source of the gas,
It is transferred to suitable pressure through pressure regulator valve, with mass flowmenter stoichiometric consumption natural gas.By in pressure, temperature transmitter monitoring reactor
Temperature and pressure.Temperature of liquid in tank is controlled by water bath with thermostatic control, thus adjusting reactor temperature.By data acquisition system
System monitors gas hydrate synthesis situation in reactor with computer data acquisition and by photocell lenses.This system working pressure is 0
～30mpa, temperature range is -10 DEG C～30 DEG C.
The preparation process of gas hydrate is as follows:
1) with particle diameter be 325 mesh graphite microparticles as raw material, graphene oxide powder is prepared using hummers method,
By weight/mass percentage composition 0.1% ~ 1% graphene oxide powder and weight/mass percentage composition be 0.3 ~ 3.5% sodium chloride
(nacl) stir 70min at a temperature of being blended in 40 ~ 60 DEG C with distilled water, make graphene oxide dispersion.
2) with vacuum pump by reactor, pipe-line system evacuation, pumpdown time about 40～50min.
3) graphene aqueous solution of the variable concentrations preparing is injected reactor, stir 3～5 min, and be first pre-chilled to
Uniform temperature.
4) open control valve for gas pipeline, High-Voltage Experimentation gas is filled with reactor, by pressure regulator valve by response system pressure
Power maintains the required pressure 0～30mpa of experiment.
5) set 1 DEG C～15 DEG C of experimental temperature, start the temperature control system of experimental provision.Using water-bath, reactor is entered
Row cooling, the temperature in reactor reaches design temperature.
6) carry out gas hydrate and generate experiment.
In experimentation, distilled water is made by oneself with rustless steel electrically heated distilling apparatuss, by the bs200s type for 0.1g for the precision
Analytical balance weighs；Graphene oxide precision is that the electronic analytical balance of 0.05mg weighs.Can be adopted in real time by computer
Collection experimental data and image.
Beneficial effects of the present invention:
(1) hydrate generation facilitation effect is good
The superpower hydrophilic of this novel hydrates accelerator, high-specific surface area, high-termal conductivity, good wettability and table
Face activity, and easy and water formation hydrogen bond, less hydrate generates the time, improves hydrate gas storage density, all for promoting to be hydrated
The generation of thing provides good environment, and effect is obvious.
(2) it is widely used
Can obtain extensively should in fields such as gas hydrate storaging and transport technology, gas hydrate isolation technics and desalinizations
With.
(3) low cost is economical good
The accelerator low cost of the present invention, consumption is few, so that the condition that hydrate generates is reduced, the time shortens, and gas-storing capacity increases
Greatly, it is effectively improved hydrate production economy benefit.
Brief description
Fig. 1 hydrate generates experimental provision flow chart.1 gas cylinder；2 pressure regulator valves；3 mass flowmenters；4 check valves；5 locks
Valve；6 vacuum pumps；7 pressure, temperature transmitter；8 waters bath with thermostatic control；9 tanks；10 reactors；11 data collecting systems；12 computers;
13 photocell lenses.
Specific embodiment
Below the present invention is further described in detail, but embodiments of the present invention are not limited to that.
The experimental provision that the present invention adopts is as shown in figure 1, by gas cylinder 1；Pressure regulator valve 2；Mass flowmenter 3；Check valve
4；Gate valve 5；Vacuum pump 6；Pressure, temperature transmitter 7；Water bath with thermostatic control 8；Tank 9；Reactor 10；Data collecting system 11；Calculate
Machine 12 grade forms.Using gas cylinder 1 as source of the gas, it is transferred to suitable pressure through pressure regulator valve 2, with mass flowmenter 3 stoichiometric consumption sky
So gas.Monitor the temperature and pressure in reactor 10 by pressure, temperature transmitter 7.Liquid in tank 9 is controlled by water bath with thermostatic control 8
Temperature, thus adjust reactor temperature.By data collecting system 11 and computer 12 gathered data and by photocell lenses
Gas hydrate synthesis situation in 13 monitoring reactors.Vacuum pump 6 is used for aspirating liquid in reactor.This system working pressure be 0～
30mpa, temperature range is -10 DEG C～50 DEG C.
Concrete preparation process:
1) with particle diameter be 325 mesh graphite microparticles as raw material, graphene oxide powder is prepared using hummers method,
By weight/mass percentage composition 0.1% ~ 1% graphene oxide powder and weight/mass percentage composition be 0.3 ~ 3.5% sodium chloride
(nacl) stir 70min at a temperature of being blended in 40 ~ 60 DEG C with distilled water, make graphene oxide dispersion.It is shown in Table 1.
2) all exclude the air in reactor and pipe-line system, with experimental gas, they are replaced twice, then take out true
Empty.
3) with vacuum pump by reactor, pipe-line system evacuation, pumpdown time about 40～50 min.
4) by the new accelerator aqueous solution injection reactor of the variable concentrations preparing, 3～5 min are stirred, and first pre-
It is as cold as uniform temperature.
5) open check valve (4), High-Voltage Experimentation gas is filled with reactor, by pressure regulator valve (2) by reacting system pressure
Maintain the required pressure of experiment.
6) set experimental temperature, start the temperature control system of experimental provision.Using water-bath (8), reactor (10) is carried out
Cooling, the temperature in reactor reaches design temperature.
7) carry out gas hydrate and form experiment.
Table 1 Graphene promoter component
Drawn by experiment under these conditions, the induction time of gas hydrate synthesis is in 2～7min；Gas storage density exists
164m3/m3More than.
Embodiment:
From Graphene accelerator consist of: graphene oxide concentration (wt%) 0.1%, sodium chloride (nacl) concentration
(wt%) 0.30.Experimental procedure is ibid.Hydrate generate equilibrium condition be temperature at 1.9～5.5 DEG C, pressure be 1.79～
3.7mpa.
Embodiment 1:
From accelerator sm1, its composition is configured to: graphene oxide concentration (wt) 0.1%, sodium chloride (nacl) concentration
(wt) 0.30%.Add deionized water to stir 70min at 50 DEG C, make graphene oxide dispersion.With methane gas in temperature
Test at 6.3 DEG C, experimental procedure is ibid.Experimental result is shown in Table 2.Experimental procedure is ibid.
Table 2 experimental result
| Experiment sequence number | Mass concentration (wt%) | Induction time (min) | Vapor pressure (mpa) |
| 1 | 0.1 | 7.56 | 3.87 |
| 2 | 0.2 | 7.37 | 3.75 |
| 3 | 0.3 | 7.02 | 2.82 |
| 4 | 0.4 | 6.78 | 2.64 |
| 5 | 0.5 | 5.89 | 2.34 |
| 6 | 0.6 | 5.54 | 2.20 |
Embodiment 2:
From accelerator sm5, its composition is configured to: graphene oxide concentration (wt) 1%, sodium chloride (nacl) concentration
(wt) 3%.Add deionized water to stir 70min at 50 DEG C, make graphene oxide dispersion.With methane gas in temperature it is
Test at 6.2 DEG C, experimental procedure is ibid.Experimental result is shown in Table 3.Experimental procedure is ibid.
Table 3 experimental result
Claims (2)
1. a kind of graphene oxide gas hydrate accelerant is it is characterised in that be graphene oxide dispersion, wherein Graphene
Weight/mass percentage composition be 0.1%～1%, the weight/mass percentage composition of sodium chloride is 0.3～3.5%, and remaining is distilled water.
2. a kind of preparation method of graphene oxide gas hydrate accelerant it is characterised in that by graphene oxide powder with
As the sodium chloride mix and blend of solvent, then it is configured to graphene oxide dispersion with distilled water；The quality hundred of wherein Graphene
Content is divided to be 0.1%～1%, the weight/mass percentage composition of sodium chloride is 0.3～3.5%.
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| CN106000229B (en) * | 2016-06-13 | 2019-03-08 | 中山大学 | The experimental system visualizing and method of visual reaction kettle and displacer gas hydrate |
| CN107400542B (en) * | 2017-09-20 | 2020-05-29 | 重庆大学 | Nano graphite fluid for enhancing purification of coal bed gas |
| CN109701444B (en) * | 2017-10-26 | 2021-12-31 | 中国科学院青岛生物能源与过程研究所 | Composite gas hydrate nano-accelerator and preparation method and application thereof |
| CN108439505B (en) * | 2018-04-20 | 2021-07-20 | 大连理工大学 | Hydrate method seawater desalination method based on graphite reinforcement |
| CN109456436B (en) * | 2018-09-27 | 2021-01-19 | 青岛科技大学 | Natural gas hydrate nano accelerator and preparation method thereof |
| CN110756121A (en) * | 2019-10-24 | 2020-02-07 | 上海理工大学 | Device and method for promoting generation of carbon dioxide hydrate |
| CN112646624A (en) * | 2020-11-30 | 2021-04-13 | 青岛科技大学 | Method for promoting efficient generation of methane hydrate by graphene composite hydrogel |
| CN112777587B (en) * | 2020-12-14 | 2022-11-04 | 中国地质大学（武汉） | Gas hydrate generation promoter and preparation method and application thereof |
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Effective date of registration: 20220707 Address after: 362268 Daxue Road, Neikeng Town, Jinjiang City, Quanzhou City, Fujian Province Patentee after: Quanzhou Vocational and Technical University Address before: 213164 No.1 Gehu Middle Road, Wujin District, Changzhou City, Jiangsu Province Patentee before: CHANGZHOU University |