CN106634860A - Supercritical carbon dioxide graphene nanofluid and preparation and application method thereof - Google Patents
Supercritical carbon dioxide graphene nanofluid and preparation and application method thereof Download PDFInfo
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- CN106634860A CN106634860A CN201610844723.9A CN201610844723A CN106634860A CN 106634860 A CN106634860 A CN 106634860A CN 201610844723 A CN201610844723 A CN 201610844723A CN 106634860 A CN106634860 A CN 106634860A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
- F25B9/008—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant being carbon dioxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B2309/00—Gas cycle refrigeration machines
- F25B2309/06—Compression machines, plants or systems characterised by the refrigerant being carbon dioxide
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Abstract
The invention discloses a supercritical carbon dioxide graphene nanofluid and a preparation method thereof. The preparation method comprises vacuumizing a mixer filled with nano graphene; then inletting high-pressure carbon dioxide into the mixer for intensively mixing with the nano graphene to obtain a gas mixture; lastly, compressing the gas mixture to a supercritical state to obtain the nanofluid. The obtained supercritical carbon dioxide graphene nanofluid is good in dispersion uniformity, high in thermal conductivity, easy to reach critical conditions, inactive in chemical properties and safe. The invention also relates to the purpose and application of the supercritical carbon dioxide graphene nanofluid which serves as a supercritical carbon dioxide Brayton cycle working medium.
Description
Technical field
The present invention relates to supercritical fluid, more particularly to a kind of supercritical carbon dioxide graphene nanofluid and its system
Preparation Method and application.
Background technology
Choi of Argonne National Laboratories of the U.S. et al. once proposed the concept of nano-fluid in nineteen ninety-five, i.e., nanometer
Powder is distributed to formation suspension in the low decentralized medium of electrical conductivity (such as water, alcohol or oil), so as to improve leading for decentralized medium
Hot property.Nano-fluid can be widely applied to the heat conduction in the fields such as vehicle, Aero-Space, electronics as a kind of novel heat transfer working medium
And cooling is required.
Graphene is carbon atom with the tightly packed cellular Colloidal particles carbon nanometer material of sp2 hybrid systems
Material.Tridimensional network is built between activated carbon granule using Graphene, the specific surface area of activated carbon can not only be improved, also
Beneficial to migration resistance of the ion in hole is reduced, heat conductivility is improved.Because Graphene has unique two-dimensional structure, excellent
Electric conductivity, outstanding mechanics and thermal property, the specific surface area of super large and opening surface so that graphene-based material exists
Application in field of radiating has great potentiality.
Although Graphene has excellent performance, still suffer from bottleneck in use, graphene nanofluid it is secondary
Dispersion is the topmost limiting factor for restricting Graphene heat conductivility.In the market existing graphene powder was being used
It is difficult to disperse again in journey, causes heat conductivility to be lifted unobvious.
The content of the invention
It is an object of the invention to solve graphene powder be difficult to disperse again in use, heat conductivility is caused to carry
Rise unconspicuous problem, there is provided a kind of heat conductivility preferably supercritical carbon dioxide graphene nanofluid and preparation method thereof
And application.
A kind of supercritical carbon dioxide graphene nanofluid is by supercritical carbon dioxide and is dispersed in carbon dioxide
In nano-graphene composition, the concentration of Graphene is 0.1wt%～2wt%, the average grain diameter of graphene particles is 1～
10nm。
For simplicity, " % (weight percent hundred) " is abbreviated as " wt% " in this specification.Above-mentioned concentration and average
The graphene dispersion of particle diameter has preferably heat conductivility in supercritical carbon dioxide, can greatly improve overcritical dioxy
Change the performance of carbon, strengthen the heat convection ability of carbon dioxide.
Further, the pressure of the nano-fluid is 8～22MPa, and the temperature of the nano-fluid is：40～800 DEG C.
It is in a supercritical state in the temperature and pressure carbon dioxide, and uniform nano-fluid is formed, can be used as overcritical two
The working medium of carbonoxide Brayton Cycle system.
The present invention also provides a kind of method for preparing above-mentioned supercritical carbon dioxide graphene nanofluid, including following step
Suddenly：
1) blender that first will be equipped with nano-graphene is vacuumized；
2) high-pressure carbon dioxide is passed through in blender again and is thoroughly mixed to form gaseous mixture with nano-graphene；
3) compress gaseous mixture and form nano-fluid to supercriticality.
The blender that will be equipped with nano-graphene is vacuumized and can further removed in blender and absorption is in nanometer stone
The gaseous impurity on black alkene surface.The vacuum of blender is 0.01～0.1MPa, and the pressure of high-pressure carbon dioxide is 5～10MPa,
High-pressure carbon dioxide is passed through in blender, higher instantaneous pressure is formed with the blender of vacuum state poor.This moment pressure
Power difference is formed " gas explosion " in blender, the nano-graphene that part is reunited can be changed into tiny particle, or even is peeled off
Become single-layer graphene, so as to substantially increase the decentralization of nano-graphene, enhance heat conductivility.
Gaseous mixture can be imported in booster pump, compression gaseous mixture to supercriticality forms nano-fluid.
Before supercritical carbon dioxide graphene nanofluid is prepared, it is possible to use vavuum pump first takes out preparation system very
Sky, then carbon dioxide is rinsed into whole preparation system, to eliminate preparation system in the other impurities that remain.
The supercritical carbon dioxide graphene nanofluid of preparation can be stored in standby in high pressure cylinder.
Further, the method for preparing supercritical carbon dioxide graphene nanofluid also comprises the steps, will
Carbon dioxide is passed through before blender, and Graphene is preheated, and preheating temperature is 40 DEG C～300 DEG C.Preheating can be further
Lift the dispersive property of Graphene.
Nano-fluid, the booster pump are formed it is possible to further compress gaseous mixture using booster pump to supercriticality
Can be plunger displacement pump or centrifugal pump.
Further, the present invention also provides above-mentioned supercritical carbon dioxide graphene nanofluid as overcritical dioxy
Change the purposes that carbon Bretton circulates working media.
Supercritical carbon dioxide Brayton cycle only needs the extraneous temperature for providing 200～800 degrees Celsius, using prior art
The temperature that can be easily reached.Supercritical carbon dioxide graphene nanofluid working medium is gaseous state and liquid and the stream deposited
Body, close to liquid, close to gas, diffusion coefficient is about more than 100 times of liquid to viscosity to density, compares overcritical titanium dioxide
Carbon working medium has more preferably heat transfer efficiency and lower energy loss, can greatly improve the performance of supercritical carbon dioxide,
Strengthen the heat convection ability of carbon dioxide, so that the efficiency of supercritical carbon dioxide Brayton cycle obtains bigger carrying
It is high.The characteristics of supercritical carbon dioxide graphene nanofluid working medium is that critical condition is more easily reachd, chemical property torpescence,
Colorless and odorless is nontoxic, safety.
Further, the present invention also provides a kind of Brayton Cycle system, including：Isentropic Compression subsystem, isobaric heating
Subsystem, constant entropy expansion subsystem and isobaric heat release subsystem, also including working media, the working media be pressure 8～
The supercritical carbon dioxide graphene nanofluid of 22MPa, 40～800 DEG C of temperature.In the nano-fluid, graphene uniform point
Dissipate in CO 2 medium, concentration is 0.1wt%～2wt%, and the average grain diameter of graphene particles is 1～10nm.
Further, the present invention also provides a kind of above-mentioned Brayton Cycle system answering in nuclear reactor electricity generation system
With.Supercritical carbon dioxide Brayton cycle as nuclear-power reactor novel energy converting system, with energy conversion efficiency
The features such as height, good security, system compact, application prospect is quite varied.
Further, the present invention also provides a kind of application of above-mentioned Brayton Cycle system in distributed generation system.
The distributed generation system includes solar energy, biomass energy and UTILIZATION OF VESIDUAL HEAT IN.Crucial and core in the distributed generation system
Heart TRT is Brayton Cycle system.
The invention has the beneficial effects as follows：Compared with prior art, the present invention is using the low viscous of supercritical carbon dioxide fluid
The special nature of degree, high diffusibility and high-solvency, CO 2 fluid is injected between graphene layer gap, forms two
The intercalation configuration of carbon oxide fluid-Graphene, further reduces the active force of graphite layers, so as to obtain the graphite of high degree of dispersion
Alkene, so as to reach the effect of high thermal conductivity energy.The specific surface area of nano-graphene is higher, the overcritical titanium dioxide of adsorption
Carbon flow body can prevent the aggregation of Graphene.
The present invention is simple to operate, will not destroy the structure and property of Graphene, and high-quality overcritical titanium dioxide can be obtained
Carbon graphite alkene nano-fluid.Also, preparation process is nontoxic, safe operation, technical process is simple, safety and environmental protection.
The present invention is described in further detail below in conjunction with drawings and Examples；But a kind of overcritical dioxy of the present invention
Change carbon graphite alkene nano-fluid and its preparation method and application and be not limited to embodiment.
Description of the drawings
Fig. 1 is the structural representation of preparation system of the present invention.
Specific embodiment
With reference to Fig. 1, the present invention includes carbon dioxide for the system for preparing supercritical carbon dioxide graphene nanofluid
Gas cylinder 1, blender 2, vavuum pump 3, booster pump 4 and high pressure cylinder 5.Dioxide bottle 1, blender 2, booster pump 4 and height
Cylinder pressure 5 is sequentially connected, and vavuum pump 3 connects blender 2 for vacuumizing to blender 2.Also set between the connecting line of system
Valve is equipped with for controlling break-make, the first valve 6, blender 2 and vacuum are provided between dioxide bottle 1 and blender 2
The second valve 7 is provided between pump 3, the 3rd valve 8 is provided between booster pump 4 and high pressure cylinder 5.3rd valve 8 is three-way valve,
The break-make of connecting line can be controlled, can be used for discharging the tail gas of cleaning equipment again.Specifically, dioxide bottle 1 can be with
It is such as dioxide bottle.Booster pump 4 can be plunger displacement pump or centrifugal pump.
Embodiment 1
The present embodiment provides a kind of method for preparing supercritical carbon dioxide graphene nanofluid, and step is as follows：
First preparation system is vacuumized using vavuum pump 3, opens dioxide bottle 1 to rinse whole using carbon dioxide
Preparation system, eliminates the other impurities remained in preparation system.
Nano-graphene of the average grain diameter for 10nm is loaded into blender 2, is evacuated in blender 2 by vavuum pump 3
0.01MPa.Graphene is carried out to be preheated to 40 DEG C, to activate graphene molecules, decentralization is lifted.Dioxide bottle 1 will be pressed
The strong high-pressure carbon dioxide for 5MPa is passed through in blender 2 and is thoroughly mixed to form gaseous mixture with nano-graphene.Control gaseous mixture
The concentration of middle Graphene is 2wt%.High-pressure carbon dioxide is passed through in blender 2, forms higher with the blender 2 of vacuum state
Instantaneous pressure is poor.This instantaneous pressure difference is formed " gas explosion " in blender, and the nano-graphene that part is reunited is changed into carefully
Little particle, in addition peel off become single-layer graphene, so as to substantially increase the decentralization of nano-graphene, enhance thermal conductivity
Energy.
Gaseous mixture is compressed with booster pump 4 form nano-fluid to supercriticality.The pressure for controlling nano-fluid is 8MPa,
Temperature is：500 DEG C, form uniform nano-fluid.The supercritical carbon dioxide graphene nanofluid of preparation is stored in into height
It is standby in cylinder pressure 5.This graphene nanofluid stable existence more than 6 months, and its thermal conductivity ratio supercritical carbon dioxide
Thermal conductivity factor improve 21%.
Using the graphene nanofluid as supercritical carbon dioxide Brayton cycle working media, further by Graphene
Nano-fluid temperature is increased to 800 DEG C, in the energy circulation for nuclear reactor electricity generation system.
Embodiment 2
The present embodiment provides a kind of method for preparing supercritical carbon dioxide graphene nanofluid, and step is as follows：
All connecting valves 6,7,8 make internal system unimpeded in opening system.System is vacuumized using vavuum pump 3.With
After close the second valve 7, using high-purity CO2Gas bleed whole system, to eliminate preparation system in remain other impurities,
Tail gas is discharged to its exterior by the 3rd valve 8.
The blender 2 that first will be equipped with nano-graphene with vavuum pump 3 is evacuated to 0.01MPa, nano-graphene it is average
Particle diameter is 1nm.Graphene is carried out to be preheated to 300 DEG C, to activate graphene molecules, decentralization is lifted.Again by carbon dioxide gas
Pressure is passed through in blender 2 for the high-pressure carbon dioxide of 10MPa and is thoroughly mixed to form gaseous mixture with nano-graphene in bottle 1.Control
The concentration of Graphene is 1wt% in gaseous mixture processed.High-pressure carbon dioxide is passed through in blender, is formed with the blender of vacuum state
Higher instantaneous pressure is poor.This instantaneous pressure difference is formed " gas explosion " in blender, and the nano-graphene that part is reunited turns
It is changed into tiny particle, or even stripping becomes single-layer graphene.
Gaseous mixture is compressed with booster pump 4 form nano-fluid to supercriticality.The pressure for controlling nano-fluid is
22MPa, temperature is：300 DEG C, form uniform nano-fluid.By the supercritical carbon dioxide graphene nanofluid storage for preparing
Exist standby in high pressure cylinder 5.The graphene nanofluid as supercritical carbon dioxide Brayton cycle working media, for core
In the energy circulation of reactor (small modules reactor) electricity generation system.This graphene nanofluid stable existence 12 months with
On, and the thermal conductivity factor of its thermal conductivity ratio supercritical carbon dioxide improves 12%.
Embodiment 3
The present embodiment provides a kind of method for preparing supercritical carbon dioxide graphene nanofluid, and step is as follows：
All connecting valves 6,7,8 make internal system unimpeded in opening system.System is vacuumized using vavuum pump 3.With
After close the second valve 7, using high-purity CO2Gas bleed whole system, to eliminate preparation system in remain other impurities,
Tail gas is discharged to its exterior by the 3rd valve 8.
The blender 2 that first will be equipped with nano-graphene is evacuated to 0.1MPa, and the average grain diameter of nano-graphene is 5nm.
Pressure is passed through in blender 2 for the high-pressure carbon dioxide of 15MPa is again thoroughly mixed to form gaseous mixture with nano-graphene.Control
The concentration of Graphene is 0.1wt% in gaseous mixture.High-pressure carbon dioxide is passed through in blender 2, the blender shape with vacuum state
It is poor into higher instantaneous pressure.
Gaseous mixture is compressed with booster pump 4 form nano-fluid to supercriticality.The pressure for controlling nano-fluid is
15MPa, temperature is：40 DEG C, form uniform nano-fluid.By the supercritical carbon dioxide graphene nanofluid storage for preparing
It is standby in high pressure cylinder 5.The graphene nanofluid as supercritical carbon dioxide Brayton cycle working media, for industry
In the energy circulation of the waste heat recovery generating system of used heat.This graphene nanofluid stable existence more than 8 months, and it leads
The thermal conductivity factor of hot coefficient ratio supercritical carbon dioxide improves 19%.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore the restriction of the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art comes
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of supercritical carbon dioxide graphene nanofluid, it is characterised in that：The fluid by supercritical carbon dioxide and
The nano-graphene composition being dispersed in carbon dioxide, pressure is 8～22MPa, and temperature is 40 DEG C～800 DEG C；Wherein receive
The concentration of rice Graphene is 0.1wt%～2wt%, and average grain diameter is 1～10nm.
2. a kind of preparation method of supercritical carbon dioxide graphene nanofluid, it is characterised in that comprise the following steps：
1) nano-graphene powder is fitted into stainless steel and is vacuumized；
2) high-pressure carbon dioxide is passed through in stainless steel and is thoroughly mixed to form gaseous mixture with nano-graphene powder；
3) compress gaseous mixture and form nano-fluid to supercriticality.
3. preparation method according to claim 2, it is characterised in that：The vacuum for vacuumizing be 0.01～
0.1MPa, the pressure of the high-pressure carbon dioxide is 5～10MPa.
4. preparation method according to claim 2, it is characterised in that：The concentration of Graphene is in the nano-fluid
0.1wt%～2wt%, average grain diameter is 1～10nm.
5. preparation method according to claim 2, it is characterised in that：The pressure of the nano-fluid is 8～22MPa, warm
Spend for 40 DEG C～800 DEG C.
6. preparation method according to claim 2, it is characterised in that：Step 1) in, also include preheating Graphene,
Preheating temperature is 40 DEG C～300 DEG C.
7. the supercritical carbon dioxide graphene nanofluid described in claim 1 is used as supercritical carbon dioxide Brayton cycle
The purposes of working media.
8. a kind of Brayton Cycle system, including：Isentropic Compression subsystem, isobaric heating subsystem, constant entropy expansion subsystem and
Isobaric heat release subsystem and working media, it is characterised in that：The working media is the overcritical dioxy described in claim 6
Change carbon graphite alkene nano-fluid.
9. application of the Brayton Cycle system described in claim 8 in nuclear reactor electricity generation system.
10. application of the Brayton Cycle system described in claim 8 in distributed generation system.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892293A (en) * | 2018-01-08 | 2018-04-10 | 韩笑峰 | A kind of method that graphene is prepared using coal as raw material |
| CN109607516A (en) * | 2018-11-26 | 2019-04-12 | 天元羲王控股有限公司 | A kind of layer graphene production equipment and its control method less |
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| CN101285657A (en) * | 2007-04-09 | 2008-10-15 | 李建民 | Supercritical fluid fluidized intensified heat diffusion method and its heat diffusion working medium and applications |
| CN103588197A (en) * | 2013-11-06 | 2014-02-19 | 华侨大学 | Preparation method for graphene nanofluid |
| CN104791204A (en) * | 2015-03-24 | 2015-07-22 | 西安交通大学 | Combined power generation system with geothermal heating, fuel gas and supercritical carbon dioxide |
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| CN1740264A (en) * | 2004-08-28 | 2006-03-01 | 鸿富锦精密工业（深圳）有限公司 | Thermally conductive material |
| CN101285657A (en) * | 2007-04-09 | 2008-10-15 | 李建民 | Supercritical fluid fluidized intensified heat diffusion method and its heat diffusion working medium and applications |
| CN103588197A (en) * | 2013-11-06 | 2014-02-19 | 华侨大学 | Preparation method for graphene nanofluid |
| CN104791204A (en) * | 2015-03-24 | 2015-07-22 | 西安交通大学 | Combined power generation system with geothermal heating, fuel gas and supercritical carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892293A (en) * | 2018-01-08 | 2018-04-10 | 韩笑峰 | A kind of method that graphene is prepared using coal as raw material |
| CN109607516A (en) * | 2018-11-26 | 2019-04-12 | 天元羲王控股有限公司 | A kind of layer graphene production equipment and its control method less |
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Application publication date: 20170510 |