CN104888673A - 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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- CN104888673A CN104888673A CN201510258514.1A CN201510258514A CN104888673A CN 104888673 A CN104888673 A CN 104888673A CN 201510258514 A CN201510258514 A CN 201510258514A CN 104888673 A CN104888673 A CN 104888673A
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- hydrate
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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 generate and utilize technical field, refer in particular to a kind of novel promoter of accelerating methane gas gas hydrate synthesis.Also the generation that can be used for other gas hydrates such as natural gas, carbon dioxide, oxygen promotes.
Background technology
At present, new technology development based on gas hydrate application not only develops rapidly at the energy, field of Environment Protection, and also achieve major progress in some other field, the solid-state conveying of such as natural gas and storage, gas hydrates as vehicle fuel, based on generate hydrate new separation technology concentrated, the admixture of gas of desalination technology, the aqueous organopolysiloxane (be separated and near critical and supercritical extract etc.) and based on the bioengineering of hydrate and field of new etc.But the application of hydrate in these fields with gas hydrate generate suppression and facilitation closely bound up, the obstruction of the factor such as be subject to that its gas storage density is low, formation speed is slow and induction time is long, the maximum technology barrier that especially current Application of Hydrate technology faces is exactly the generating rate and the efficiency that how to improve hydrate.Such as methane pressure in static pure aquatic system be 5.76MPa, when temperature is 4.3 DEG C, form the induction time of hydrate more than 28 hours, the speed of growth of hydrate crystal directly affects the popularization that hydrate utilizes technology slowly.For addressing these problems, have employed the formation (Lin Yula etc. that multiple method promotes hydrate, chemical industry is in progress, 2005,24(11): 1229-1233): by stirring the speed of growth that can improve hydrate, but stirring brings again some other unfavorable factors: energy ezpenditure increase, the reduction of hydrate gas storage density etc.; Adopt ultrasonic atomization, increase air-water contact area, hydrate formation speed can be improved, but the ultrasonic ultrasonic delay line memory that system is added not only makes investment cost increase, and operating cost also increases; Spray and bubble method can increase phase contact area, thus improve hydrate formation speed; In gas hydrate synthesis system, add some additives can promote that hydrate generates, improve hydrate growth speed, what domestic and international research was more is add anion surfactant in water, as lauryl sodium sulfate (SDS), oxolane (THF), neopelex (SDBS), APG (APG) and Tween series of surfactants and composite additive etc.Gas hydrate synthesis induction time can be made to shorten to 1 ~ 1.5 hour, and pressure comparatively pure aquatic system reduces by 1 ~ 2 MPa.But, although this kind of surfactant can make hydrate formation speed accelerate, but can not be satisfactory, and hydrate gas storage density is not high.Therefore, research novel hydrates promoter for generation is the only way advancing hydrate industrialization.
Summary of the invention
The object of the invention is to provide a kind of novel hydrates promoter graphene oxide powder for the deficiencies in the prior art, present invention process is simple, with low cost, operating condition is easily controlled, and 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.Superhydrophilic surface refers to the surface with the contact angle < 5 ° of water, its excellent performance, is widely used, and can realize self-cleaning surface, improve the several functions such as surface heat exchange efficiency.The similar graphite surface of Graphene, can the various atom of adsorption and desorption and molecule.There is high strength, high conductivity, high-specific surface area, high-termal conductivity.The feature of graphene oxide structural model is that single-layer graphene oxide keeps planar structure substantially, carbon-carbon double bond forms similar aromatic ring structure, and be connected with hydroxyl and this Liang Zhong functional group of epoxy radicals, also have part carboxyl at the edge of planar structure, and the existence of carboxyl and hydroxyl makes itself and water molecule energy form hydrogen bond simultaneously.Containing chemical groups such as carboxyl, hydroxyl, carboxyl and epoxy radicals in graphene oxide, make graphene oxide have extremely strong hydrophily, there is good wettability and surface-active.Micro-oxidation Graphene can be added in water according to these characteristics, to strengthen the contact area of natural gas and hydrone and gas solubility in the liquid phase and the formation of hydrogen bond, accelerate gas hydrate generating rate.In addition, the thermal conductivity that graphene oxide is given prominence to also accelerates the heat trnasfer of hydrate reaction of formation, heat can be evacuated rapidly, when hydrate at air-water Surface Creation time, its good thermal conductivity can accelerate thermal diffusion effect, and the latent heat that generation hydrate is discharged does not affect the growth of hydrate.
For achieving the above object, the present invention adopts following technical scheme:
Graphene oxide powder is preparing the purposes in gas hydrate accelerant.
A kind of graphene oxide gas hydrate accelerant, be graphene oxide dispersion, wherein Graphene (solid) mass percentage is 0.1% ~ 1%, and sodium chloride (NaCl) mass percentage is 0.3 ~ 3.5%, and all the other are distilled water.
The preparation method of described gas hydrate accelerant is: using graphene oxide powder and sodium chloride (NaCl) mix and blend as solvent, then be mixed with graphene oxide dispersion with distilled water.
Described graphene oxide powder can with particle diameter be 325 object graphite microparticles for raw material, adopt Hummers method to prepare.
The preparation facilities that the present invention adopts comprises gas cylinder, pressure regulator valve, mass flowmenter, control valve, vavuum pump, pressure, temperature transmitter, water bath with thermostatic control, tank, reactor, data collecting system, computer etc.By gas cylinder as source of the gas, be transferred to suitable pressure through pressure regulator valve, with mass flowmenter stoichiometric consumption natural gas.By the temperature and pressure in pressure, temperature transmitter monitoring reactor.Control fluid temperature in tank by water bath with thermostatic control, thus regulate reactor temperature.By data collecting system and computer data acquisition and by gas hydrate synthesis situation in photocell lens monitoring reactor.This system working pressure is 0 ~ 30MPa, and temperature range is-10 DEG C ~ 30 DEG C.
The preparation process of gas hydrate is as follows:
1) be that 325 object graphite microparticles are for raw material with particle diameter, Hummers method is adopted to prepare graphene oxide powder, by mass percentage 0.1% ~ 1% graphene oxide powder and mass percentage be 0.3 ~ 3.5% sodium chloride (NaCl) and distilled water be blended in 40 ~ 60 DEG C of temperature under stir 70min, make graphene oxide dispersion.
2) with vavuum pump, reactor, pipe-line system are vacuumized, pumpdown time about 40 ~ 50 min.
3) graphene aqueous solution of the variable concentrations prepared 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, reacting system pressure maintained the pressure 0 ~ 30MPa needed for experiment by pressure regulator valve.
5) set experimental temperature 1 DEG C ~ 15 DEG C, start the temperature control system of experimental provision.Water-bath is utilized to cool reactor, until the temperature in reactor reaches design temperature.
6) carry out gas hydrate and generate experiment.
In experimentation, distilled water stainless steel electrical distiller self-control, the BS200S type analysis balance being 0.1g by precision takes; Graphene oxide precision is that the electronic analytical balance of 0.05mg takes.Can Real-time Collection experimental data and image by computer.
beneficial effect of the present invention:
(1) hydrate generation facilitation is effective
The hydrophily that this novel hydrates promoter is superpower, high-specific surface area, high-termal conductivity, good wettability and surface-active, and Yi Yushui forms hydrogen bond, the less hydrate rise time, improve hydrate gas storage density, be all promote that the generation of hydrate provides good environment, and successful.
(2) be widely used
Can be used widely in fields such as gas hydrate storaging and transport technology, gas hydrate isolation technics and desalinizations.
(3) cost is low, economical good
Promoter cost of the present invention is low, and consumption is few, and the condition that hydrate is generated reduces, time shorten, and gas-storing capacity increases, and effectively improves hydrate production economy benefit.
Accompanying drawing explanation
Fig. 1 hydrate generates experimental provision flow chart.1 gas cylinder; 2 pressure regulator valves; 3 mass flowmenters; 4 check valves; 5 gate valves; 6 vavuum pumps; 7 pressure, temperature transmitter; 8 waters bath with thermostatic control; 9 tanks; 10 reactors; 11 data collecting systems; 12 computers; 13 photocell lenses.
Detailed description of the invention
Below the present invention is further described in detail, but embodiments of the present invention are not limited in this.
The present invention adopt experimental provision as shown in Figure 1, by gas cylinder 1; Pressure regulator valve 2; Mass flowmenter 3; Check valve 4; Gate valve 5; Vavuum pump 6; Pressure, temperature transmitter 7; Water bath with thermostatic control 8; Tank 9; Reactor 10; Data collecting system 11; Composition such as computer 12 grade.Using gas cylinder 1 as source of the gas, be transferred to suitable pressure through pressure regulator valve 2, with mass flowmenter 3 stoichiometric consumption natural gas.By the temperature and pressure in pressure, temperature transmitter 7 monitoring reactor 10.Control fluid temperature in tank 9 by water bath with thermostatic control 8, thus regulate reactor temperature.By data collecting system 11 and computer 12 image data and by gas hydrate synthesis situation in photocell lens 13 monitoring reactor.Vavuum pump 6 is used for aspirating liquid in reactor.This system working pressure is 0 ~ 30MPa, and temperature range is-10 DEG C ~ 50 DEG C.
Concrete preparation process:
1) be that 325 object graphite microparticles are for raw material with particle diameter, Hummers method is adopted to prepare graphene oxide powder, by mass percentage 0.1% ~ 1% graphene oxide powder and mass percentage be 0.3 ~ 3.5% sodium chloride (NaCl) and distilled water be blended in 40 ~ 60 DEG C of temperature under stir 70min, make graphene oxide dispersion.In table 1.
2) all get rid of the air in reactor and pipe-line system, by experimental gas, twice is replaced to them, then vacuumize.
3) with vavuum pump, reactor, pipe-line system are vacuumized, pumpdown time about 40 ~ 50 min.
4) the novel promoter aqueous solution of the variable concentrations prepared is injected reactor, stir 3 ~ 5 min, and be first pre-chilled to uniform temperature.
5) open check valve (4), High-Voltage Experimentation gas is filled with reactor, reacting system pressure maintained the pressure needed for experiment by pressure regulator valve (2).
6) set experimental temperature, start the temperature control system of experimental provision.Water-bath (8) is utilized to cool reactor (10), until the temperature in reactor reaches design temperature.
7) carry out gas hydrate and form experiment.
Table 1 Graphene promoter component
Draw by experiment under these conditions, the induction time of gas hydrate synthesis is at 2 ~ 7min; Gas storage density is at 164m
3/ m
3above.
Embodiment:
The Graphene promoter of selecting consists of: graphene oxide concentration (wt%) 0.1%, sodium chloride (NaCl) concentration (wt%) 0.30.Experimental procedure is the same.Hydrate generate equilibrium condition be temperature at 1.9 ~ 5.5 DEG C, pressure is 1.79 ~ 3.7Mpa.
embodiment 1:
The promoter SM1 selected, its composition is configured to: graphene oxide concentration (wt) 0.1%, sodium chloride (NaCl) concentration (wt) 0.30%.Add deionized water and stir 70min at 50 DEG C, make graphene oxide dispersion.Test at temperature is 6.3 DEG C with methane gas, experimental procedure is the same.Experimental result is in table 2.Experimental procedure is the same.
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:
The promoter SM5 selected, its composition is configured to: graphene oxide concentration (wt) 1%, sodium chloride (NaCl) concentration (wt) 3%.Add deionized water and stir 70min at 50 DEG C, make graphene oxide dispersion.Test at temperature is 6.2 DEG C with methane gas, experimental procedure is the same.Experimental result is in table 3.Experimental procedure is the same.
Table 3 experimental result
Claims (3)
1. graphene oxide powder is preparing the purposes in gas hydrate accelerant.
2. a graphene oxide gas hydrate accelerant, is characterized in that, is graphene oxide dispersion, and wherein Graphene mass percentage is 0.1% ~ 1%, and sodium chloride is mass percentage is 0.3 ~ 3.5%, and all the other are distilled water.
3. a preparation method for graphene oxide gas hydrate accelerant, is characterized in that, using graphene oxide powder and the sodium chloride mix and blend as solvent, then is mixed with graphene oxide dispersion with distilled water; Wherein Graphene mass percentage is 0.1% ~ 1%, and sodium chloride is mass percentage is 0.3 ~ 3.5%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000229A (en) * | 2016-06-13 | 2016-10-12 | 中山大学 | Visual reaction kettle and visualized experimental system and method for replacing natural gas hydrate |
| CN107400542A (en) * | 2017-09-20 | 2017-11-28 | 重庆大学 | A kind of nano-graphite fluid for being used to strengthen coal bed gas purification |
| CN108439505A (en) * | 2018-04-20 | 2018-08-24 | 大连理工大学 | A kind of desalination of sea water by hydrate method method strengthened based on graphite |
| CN109456436A (en) * | 2018-09-27 | 2019-03-12 | 青岛科技大学 | Gas hydrates nanometer promotor and preparation method thereof |
| CN109701444A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院青岛生物能源与过程研究所 | A kind of compound gas hydrate nanometer promotor and its preparation method and application |
| 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 |
| CN112777587A (en) * | 2020-12-14 | 2021-05-11 | 中国地质大学（武汉） | Gas hydrate generation promoter and preparation method and application thereof |
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| CN102827315A (en) * | 2012-08-30 | 2012-12-19 | 合肥工业大学 | Graphene oxide/polystyrene nano composite and preparation method thereof |
| JP2014201492A (en) * | 2013-04-05 | 2014-10-27 | 国立大学法人北海道大学 | Method for manufacturing a graphene oxide-containing liquid and uses of the same |
| CN104264260A (en) * | 2014-07-28 | 2015-01-07 | 四川大学 | Graphene/nanometer cellulose composite fibers and preparation method thereof |
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| CN102827315A (en) * | 2012-08-30 | 2012-12-19 | 合肥工业大学 | Graphene oxide/polystyrene nano composite and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106000229A (en) * | 2016-06-13 | 2016-10-12 | 中山大学 | Visual reaction kettle and visualized experimental system and method for replacing natural gas hydrate |
| CN107400542A (en) * | 2017-09-20 | 2017-11-28 | 重庆大学 | A kind of nano-graphite fluid for being used to strengthen coal bed gas purification |
| CN109701444A (en) * | 2017-10-26 | 2019-05-03 | 中国科学院青岛生物能源与过程研究所 | A kind of compound gas hydrate nanometer promotor and its preparation method and application |
| 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 |
| CN108439505A (en) * | 2018-04-20 | 2018-08-24 | 大连理工大学 | A kind of desalination of sea water by hydrate method method strengthened based on graphite |
| CN108439505B (en) * | 2018-04-20 | 2021-07-20 | 大连理工大学 | Hydrate method seawater desalination method based on graphite reinforcement |
| CN109456436A (en) * | 2018-09-27 | 2019-03-12 | 青岛科技大学 | Gas hydrates nanometer promotor and preparation method thereof |
| 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 |
| CN112777587A (en) * | 2020-12-14 | 2021-05-11 | 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 |